Catalyst and methods for polymerizing cycloolefins

ABSTRACT

Methods for the addition polymerization of cycloolefins using a cationic Group 10 metal complex and a weakly coordinating anion of the formula: 
     
       
         [(R′) z M(L′) x (L″) y ] b [WCA] d   
       
     
     wherein [(R′) z M(L′) x (L″) y ] is a cation complex where M represents a Group 10 transition metal; R′ represents an anionic hydrocarbyl containing ligand; L′ represents a Group 15 neutral electron donor ligand; L″ represents a labile neutral electron donor ligand; x is 1 or 2; and y is 0, 1, 2, or 3; and z is 0 or 1, wherein the sum of x, y, and z is 4; and [WCA] represents a weakly coordinating counteranion complex; and b and d are numbers representing the number of times the cation complex and weakly coordinating counteranion complex are taken to balance the electronic charge on the overall catalyst complex.

This is a Provisional Applications 60/103,120 Oct. 5, 1998 and60/111,590 Dec. 9, 1998.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to methods for the addition polymerizationof cycloolefins using a cationic Group 10 metal complex and a weaklycoordinating counteranion.

BACKGROUND OF THE INVENTION

Polycyclic addition polymers having directly linked polycyclic repeatingunits without any internal backbone unsaturation are desirous from thestandpoint of their inherent thermal oxidative stability and high glasstransition temperature (Tg) profiles. Recent objectives in synthesishave focused on incorporating pendant functional substituents onto thepolycyclic backbone, enabling this class of polymer to be utilized for awide variety of uses. These objectives have been successfully met inpart because of the advent of late transition metal catalysts and theirtolerance to functional groups. An increasingly important use for suchpolymers has been in the manufacture of microelectronic and opticaldevices. An important consideration in the manufacturing of polymers formicroelectronic and optical applications is polymer purity. Whilespecific classes of transition metal catalysts are tolerant tofunctional groups, there is a trade off in that monomer to catalystratios must be high in order to overcome the poisoning effects of thefunctional group on the catalyst. Consequently, many polymers containmetallic residues as a result of the high catalyst loading in thereaction medium. Traces of transition metals have been shown to catalyzethe thermal oxidative degradation of polymers. In addition, metalresidues in the polymer also deleteriously affect the polymer propertiesby raising the dielectric constant of the polymer and interfere withlight transmittance through the polymer matrix. In order to be usefulthe residual metals must be removed from the polymer to below anacceptable level.

One method of catalyzing the polymerization of cycloolefins is throughthe use of cationic transition metal complexes. Goodall et al. (U.S.Pat. No. 5,569,730) describe a method for polymerizing cycloolefinsmonomers such as norbornene and hydrocarbyl substituted norbornene-typemonomers in the presence of a chain transfer agent and a single ormulticomponent catalyst system capable of providing a Group VIIItransition metal cation source. The preferred single component catalystconsists of a transition metal cation complex containing an allyl ligandand a weakly coordinating counteranion. The multicomponent catalystsystem employs a Group VIII transition metal ion source, anorganoaluminum compound and an optional component selected from Lewisacids, strong BrØnsted acids, electron donor compounds, and halogenatedorganic compounds. The monomer to Group VIII transition metal molarratios are broadly disclosed to range from 1000:1 to 100,000:1, with apreferred range of 3000:1 to 10,000:1.

Goodall et al.(U.S. Pat. No. 5,705,503) and McIntosh et al. (WO97/20871) disclose that norbornene-type monomers containing functionalsubstituents can be successfully polymerized with single andmulticomponent transition metal catalysts of the classes disclosed inthe '730 patent supra. However, the molar ratio of monomer to Group VIIItransition metal ranges from 20:1 to 100,000:1. In fact the highestmonomer to Group VIII metal ratio actually employed is only about 5000:1which is exemplified in Example 15 of the '503 specification.

In addition to the Group VIII single and multicomponent catalyst systemsdisclosed supra, Goodall et al. (WO 97/33198) disclose a singlecomponent catalyst system suitable for polymerizing functionallysubstituted norbornene-type monomers. The single component catalystcomprises nickel, a two electron donor ligand (preferably a π-areneligand) and a pentafluorophenyl ligand. The disclosed molar ratio ofmonomer to nickel ranges from 2000:1 to 100:1.

In view of the foregoing it is apparent that a relatively high catalystloading (based on the Group VIII metal content) is necessary for thepolymerization reaction to proceed efficiently. A higher catalystloading in the monomer at the onset of the polymerization reaction,however, means that a higher residual metal content will be present inthe polymer product. Residual metals are difficult and expensive toremove. Therefore there is a need for a high activity transition metalcatalyst system capable of polymerizing substituted and unsubstitutedcycloolefin monomers.

SUMMARY OF THE INVENTION

Accordingly, it is a general object of the invention to provide apolymerizable polycycloolefin composition comprising a high activitycatalyst system.

It is another object of the invention to provide polymers with lowlevels of residual Group 10 metals.

It is a further object of the invention to provide a process forpolymerizing polycycloolefin monomers in contact with a high activityGroup 10 catalyst.

It is another object of the invention to provide a process forpolymerizing polycycloolefin monomers in solution in contact with a highactivity Group 10 catalyst system.

It is still another object of the invention to provide a process forpolymerizing polycycloolefin monomers in mass in contact with a highactivity Group 10 catalyst system.

It is another object of the invention to provide a high activity singleor multicomponent Group 10 catalyst system for the polymerization ofpolycycloolefin monomers.

It still is a further object of the invention to provide a two componentcatalyst Group 10 system comprising a procatalyst and an activator.

These and other objects of the invention are accomplished by contactinga polymerizable polycycloolefin monomer charge with a high activitycatalyst system comprising a Group 10 metal cation complex and a weaklycoordinating counteranion complex of the formula:

[(R)_(z)′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)

wherein M represents a Group 10 transition metal; R′ represents ananionic hydrocarbyl containing ligand; L′ represents a Group 15 neutralelectron donor ligand; L″ represents a labile neutral electron donorligand; z is 0 or 1; x is 1 or 2; y is 0, 1, 2, or 3, and the sum of x,y, and z equals 4; and b and d are numbers representing the number oftimes the cation complex and weakly coordinating counteranion complex(WCA), respectively, are taken to balance the electronic charge on theoverall catalyst complex. The monomer charge can be neat or in solution,and is contacted with a preformed catalyst of the foregoing formula.Alternatively, the catalyst can be formed in situ by admixing thecatalyst forming components in the monomer charge.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents an Oakridge Thermal Ellipsoid Plot (ORTEP) of(allyl)palladium(tricyclohexylphosphine)(triflate).

FIG. 2 represents an ORTEP of(allyl)palladium(tri-o-tolylphosphine)(triflate).

FIG. 3 represents an ORTEP of(allyl)palladium(tri-naphthylphosphine)(triflate)

DETAILED DESCRIPTION OF THE INVENTION Catalyst System

The catalyst of the invention comprises a Group 10 metal cation complexand a weakly coordinating counteranion complex represented by Formula Ibelow:

[(R)_(z)′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  I

wherein M represents a Group 10 transition metal; R′ represents ananionic hydrocarbyl ligand; L′ represents a Group 15 neutral electrondonor ligand; L″ represents a labile neutral electron donor ligand; x is1 or 2; y is 0, 1, 2, or 3, wherein the sum of x, y, and z is 4; and band d are numbers representing the number of times the cation complexand weakly coordinating counteranion complex (WCA), respectively, aretaken to balance the electronic charge of the overall catalyst complex.

The weakly coordinating counteranion complex is an anion which is onlyweakly coordinated to the cation complex. It is sufficiently labile tobe displaced by a neutral Lewis base, solvent or monomer. Morespecifically, the WCA anion functions as a stabilizing anion to thecation complex and does not transfer to the cation complex to form aneutral product. The WCA anion is relatively inert in that it isnon-oxidative, non-reducing, and non-nucleophilic.

An anionic hydrocarbyl ligand is any hydrocarbyl ligand which whenremoved from the metal center M in its closed shell electronconfiguration, has a negative charge.

A neutral electron donor is any ligand which when removed from the metalcenter M in its closed shell electron configuration, has a neutralcharge.

A labile neutral electron donor ligand is any ligand which is not asstrongly bound to metal center M, is easily displaced therefrom, andwhen removed from the metal center in its closed shell electronconfiguration has a neutral charge.

In the cation complex above, M represents a Group 10 metal selected fromnickel, palladium, and platinum, with palladium being the most preferredmetal.

Representative anionic hydrocarbyl containing ligands defined under R′include hydrogen, linear and branched C₁-C₂₀ alkyl, C₅-C₁₀ cycloalkyl,linear and branched C₂-C₂₀ alkenyl, C₆-C₁₅ cycloalkenyl, allylic ligandsor canonical forms thereof, C₆-C₃₀ aryl, C₆-C₃₀ heteroatom containingaryl, and C₇-C₃₀ aralkyl, each of the foregoing groups can be optionallysubstituted with hydrocarbyl and/or heteroatom substituents preferablyselected from linear or branched C₁-C₅ alkyl, linear or branched C₁-C₅haloalkyl, linear or branched C₂-C₅ alkenyl and haloalkenyl, halogen,sulfur, oxygen, nitrogen, phosphorus, and phenyl optionally substitutedwith linear or branched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl,and halogen, R′ also represents anionic hydrocarbyl containing ligandsof the formula R″C(O)O, R″C(O)CHC(O)R″, R″C(O)S, R″C(S)O, R″C(S)S, R″O,R″₂N, wherein R″ is the same as R′ defined immediately above.

The foregoing cycloalkyl, and cycloalkenyl ligands can be monocyclic ormulticyclic. The aryl ligands can be a single ring (e.g., phenyl) or afused ring system (e.g., naphthyl). In addition, any of the cycloalkyl,cycloalkenyl and aryl groups can be taken together to form a fused ringsystem. Each of the monocyclic, multicyclic and aryl ring systemsdescribed above optionally can be monosubstituted or multisubstitutedwith a substituent independently selected from hydrogen, linear andbranched C₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl, linear andbranched C₁-C₅ alkoxy, halogen selected from chlorine, fluorine, iodineand bromine, C₅-C₁₀ cycloalkyl, C₆-C₁₅ cycloalkenyl, and C₆-C₃₀ aryl. Anexample of a multicycloalkyl moiety is a norbornyl ligand. An example ofa multicycloalkenyl moiety is a norbornenyl ligand. Examples of arylligand groups include phenyl and naphthyl. For purposes of illustrationStructure I below represents a cationic complex wherein R′ is acycloalkenyl ligand derived from 1,5-cyclooctadiene. Structures II andIII illustrate cationic complexes wherein R′ represents multicycloalkyland multicycloalkenyl ligands, respectively. In Structure III thenorbornenyl ligand is substituted with a alkenyl group.

wherein M, L′, L″, x and y are as previously defined.

Additional examples of cationic complexes where R′ represents a ringsystem is illustrated in Structures IV to IVc below.

wherein M, L′, L″, x and y are as previously defined.

In another embodiment of the invention R′ represents a hydrocarbylligand containing a terminal group that coordinates to the Group 10metal. The terminal coordination group containing hydrocarbyl ligand arerepresented by the formula —C_(d′)H_(2d′)X→, wherein d′ represents thenumber of carbon atoms in the hydrocarbyl backbone and is an integerfrom 3 to 10, and X→ represents an alkenyl or heteroatom containingmoiety that coordinates to the Group 10 metal center. The ligandtogether with the Group 10 metal forms a metallacycle or heteroatomcontaining metallacycle. Any of the hydrogen atoms on the hydrocarbylbackbone in the formulae above can be independently replaced by asubstituent selected from R^(1′), R^(2′), and R^(3′) which are definedbelow.

A cation complex of the terminal coordination group containinghydrocarbyl metallacycle embodiment is represented by Structure V shownbelow:

wherein M, L′, L″, d′, x and y are as previously defined, and Xrepresents a radical selected from the group —CHR^(4′)═CHR^(4′),—OR^(4′), —SR^(4′), —N(R^(4′))₂, —N═NR^(4′), —P(R^(4′))₂, —C(O)R^(4′),—C(R^(4′))═NR^(4′), —C(O)OR^(4′), —OC(O)OR^(4′), —OC(O)R^(4′), andR^(4′) represents hydrogen, halogen, linear and branched C₁-C₅ alkyl,linear and branched C₁-C₅ haloalkyl, C₅-C₁₀ cycloalkyl, linear orbranched C₂-C₅ alkenyl, linear or branched C₂-C₅ haloalkenyl,substituted and unsubstituted C₆-C₁₈ aryl, and substituted andunsubstituted C₇-C₂₄ aralkyl.

The substituted terminal group containing hydrocarbyl metallacycles canbe represented by structure Va, below.

wherein M, L′, L″, X, x and y are as previously defined, n represents aninteger from 1 to 8 and R^(1′), R^(2′), and R^(3′) independentlyrepresent hydrogen, linear and branched C₁-C₅ alkyl, linear and branchedC₁-C₅ haloalkyl, linear or branched C₂-C₅ alkenyl, linear and branchedC₂-C₅ haloalkenyl, substituted and unsubstituted C₆-C₃₀ aryl,substituted and unsubstituted C₇-C₃₀ aralkyl, and halogen. Any ofR^(1′), R^(2′), and R^(3′) can be taken together along with the carbonatoms to which they are attached can form a substituted or unsubstitutedaliphatic C₅-C₂₀ monocyclic or polycyclic ring system, a substituted orunsubstituted C₆-C₁₀ aromatic ring system, a substituted andunsubstituted C₁₀-C₂₀ fused aromatic ring system, and combinationsthereof. When substituted, the rings described above can containmonosubstitution or multisubstitution where the substituents areindependently selected from hydrogen, linear and branched C₁-C₅ alkyl,linear and branched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy,and halogen selected from chlorine, fluorine, iodine and bromine. InStructure Va above it should be noted that when n is 0, X is bonded tothe carbon atom that contains the R^(2′) substituent.

Representative terminal group containing hydrocarbyl metallacycle cationcomplexes wherein the substituents are taken together to representaromatic and aliphatic ring systems are illustrated below underStructures Vb and Vc.

Additional examples of terminal group containing hydrocarbylmetallacycle cation complexes wherein any of R^(1′) to R^(3′) can betaken together to form aromatic ring systems are set forth in StructuresVd to Vg below.

Illustrative examples of cation complexes containing polycyclicaliphatic ring systems are set forth under structures Vh, Vi, and Vjbelow:

In Structures V through Vj above, n′ is an integer from 0 to 5; and X,M, L′, L″, “a”, n, x, y, R^(1′) and R^(4′), are as previously defined,and R^(5′) and R^(6′) independently represent hydrogen, and linear andbranched C₁-C₁₀ alkyl, R^(5′) and R^(6′) together with the carbon atomsto which they are attached can form a saturated and unsaturated cyclicgroup containing 5 to 15 carbon atoms.

Examples of heteroatom containing aryl ligands under R′ are pyridinyland quinolinyl ligands.

The allyl ligand in the cationic complex can be represented by thefollowing structure:

wherein R^(20′), R^(21′), and R^(22′) each independently representhydrogen, halogen, linear and branched C₁-C₅ alkyl, C₅-C₁₀ cycloalkyl,linear and branched C₁-C₅ alkenyl, C₆-C₃₀ aryl, C₇-C₃₀ aralkyl, eachoptionally substituted with a substituent selected from linear andbranched C₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl, halogen, andphenyl which can optionally be substituted with linear and branchedC₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl, and halogen. Any twoof R^(20′), R^(21′), and R^(22′) can be linked together with the carbonatoms to which they are attached to form a cyclic or multicyclic ring,each optionally substituted with linear or branched C₁-C₅ alkyl, linearor branched C₁-C₅ haloalkyl, and halogen. Examples of allylic ligandssuitable in the cationic complexes of the invention include but are notlimited to allyl, 2-chloroallyl, crotyl, 1,1-dimethyl allyl,2-methylallyl, 1-phenylallyl, 2-phenylallyl, and β-pinenyl.

Representative cationic complexes containing an allylic ligand are shownbelow.

In Structures VI, VIa, and VIb M, L′, L″, x and y are as previouslydefined.

Additional examples of allyl ligands are found in R. G. Guy and B. L.Shaw, Advances in Inorganic Chemistry and Radiochemistry, Vol. 4,Academic Press Inc., New York, 1962; J. Birmingham, E. de Boer, M. L. H.Green, R. B. King, R. Köster, P. L. I. Nagy, G. N. Schrauzer, Advancesin Organometallic Chemistry, Vol. 2, Academic Press Inc., New York,1964; W. T. Dent, R. Long and A. J. Wilkinson, J. Chem. Soc., (1964)1585; and H. C. Volger, Rec. Trav. Chim. Pay Bas, 88 (1969) 225; whichare all hereby incorporated by reference.

Representative neutral electron donor ligands under L′ include amines,pyridines organophosphorus containing compounds and arsines andstibines, of the formula:

E(R^(7′))₃

wherein E is arsenic or antimony, and R^(7′) is independently selectedfrom hydrogen, linear and branched C₁-C₁₀ alkyl, C₅-C₁₀ cycloalkyl,linear and branched C₁-C₁₀ alkoxy, allyl, linear and branched C₂-C₁₀alkenyl, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₆-C₁₂ arylsufides (e.g., PhS),C₇-C₁₈ aralkyl, cyclic ethers and thioethers, tri(linear and branchedC₁-C₁₀ alkyl)silyl, tri(C₆-C₁₂ aryl)silyl, tri(linear and branchedC₁-C₁₀ alkoxy)silyl, triaryloxysilyl, tri(linear and branched C₁-C₁₀alkyl)siloxy, and tri(C₆-C₁₂ aryl)siloxy, each of the foregoingsubstituents can be optionally substituted with linear or branched C₁-C₅alkyl, linear or branched C₁-C₅ haloalkyl, C₁-C₅ alkoxy, halogen, andcombinations thereof. Representative alkyl groups include but are notlimited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,decyl, and dodecyl. Representative cycloalkyl groups include but are notlimited to cyclopentyl and cyclohexyl. Representative alkoxy groupsinclude but are not limited to methoxy, ethoxy, and isopropoxy.Representative cyclic ether and cyclic thioether groups include but arenot limited furyl and thienyl, respectively. Representative aryl groupsinclude but are not limited to phenyl, o-tolyl, and naphthyl.Representative aralkyl groups include but are not limited to benzyl, andphenylethyl (i.e., —CH₂CH₂PH). Representative silyl groups include butare not limited to triphenylsilyl, trimethylsilyl, and triethylsilyl. Asin the general definition above each of the foregoing groups can beoptionally substituted with linear or branched C₁-C₅ alkyl, linear orbranched C₁-C₅ haloalkyl, and halogen.

Representative pyridines include lutidine (including 2,3-; 2,4-; 2,5-;2,6-; 3,4-; and 3,5-substituted), picoline (including 2-,3-, or4-substituted), 2,6-di-t-butylpyridine, and 2,4-di-t-butylpyridine.

Representative arsines include triphenylarsine, triethylarsine, andtriethoxysilylarsine.

Representative stibines include triphenylstibine andtrithiophenylstibine.

Suitable amine ligands can be selected from amines of the formulaN(R^(8′))₃, wherein R^(8′) independently represents hydrogen, linear andbranched C₁-C₂₀ alkyl, linear and branched C₁-C₂₀ haloalkyl, substitutedand unsubstituted C₃-C₂₀ cycloalkyl, substituted and unsubstitutedC₆-C18 aryl, and substituted and unsubstituted C₇-C₁₈ aralkyl. Whensubstituted, the cycloalkyl, aryl and aralkyl groups can bemonosubstituted or multisubstituted, wherein the substituents areindependently selected from hydrogen, linear and branched C₁-C₁₂ alkyl,linear and branched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy,C₆-C₁₂ aryl, and halogen selected from chlorine, bromine, and fluorine.Representative amines include but are not limited to ethylamine,triethylamine, diisopropylamine, tributylamine, N,N-dimethylaniline,N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-4-t-octylaniline, andN,N-dimethyl-4-hexadecylaniline.

The organophosphorus containing ligands include phosphines, phosphites,phosphonites, phosphinites and phosphorus containing compounds of theformula:

P(R^(7′))_(g)[X′(R^(7′))_(h)]_(3−g)

wherein X′ is oxygen, nitrogen, or silicon, R^(7′) is as defined aboveand each R^(7′) substituent is independent of the other, g is 0, 1, 2,or 3, and h is 1, 2, or 3, with the proviso that when X′ is a siliconatom, h is 3, when X′ is an oxygen atom h is 1, and when X′ is anitrogen atom, h is 2. When g is 0 and X′ is oxygen, any two or 3 ofR^(7′) can be taken together with the oxygen atoms to which they areattached to form a cyclic moiety. When g is 3 any two of R^(7′) can betaken together with the phosphorus atom to which they are attached torepresent a phosphacycle of the formula:

wherein R7′ is as previously defined and h′ is an integer from 4 to 11.

The organophosphorus compounds can also include bidentate phosphineligands of the formulae:

wherein R⁷ is as previously defined and i is 0, 1, 2, or 3 are alsocontemplated herein.

Representative phosphine ligands include, but are not limited totrimethylphosphine, triethylphosphine, tri-n-propylphosphine,triisopropylphosphine, tri-n-butylphosphine, tri-sec-butylphosphine,tri-i-butylphosphine, tri-t-butylphosphine, tricyclopentylphosphine,triallylphosphine, tricyclohexylphosphine, triphenylphosphine,trinaphthylphosphine, tri-p-tolylphosphine, tri-o-tolylphosphine,tri-m-tolylphosphine, tribenzylphosphine,tri(p-trifluoromethylphenyl)phosphine, tris(trifluoromethyl)phosphine,tri(p-fluorophenyl)phosphine, trin-trifluoromethylphenyl)phosphine,allyldiphenylphosphine, benzyldiphenylphosphine, bis(2-furyl)phosphine,bis(4-methoxyphenyl)phenylphosphine, bis(4-methylphenyl)phosphine,bis(3,5-bis(trifluoromethyl)phenyl)phosphine,t-butylbis(trimethylsilyl)phosphine, t-butyldiphenylphosphine,cyclohexyldiphenylphosphine, diallylphenylphosphine, dibenzylphosphine,dibutylphenylphosphine, dibutylphosphine, di-t-butylphosphine,dicyclohexylphosphine, diethylphenylphosphine, di-i-butylphosphine,dimethylphenylphosphine, dimethyl(trimethylsilyl)phosphine,diphenylphosphine, diphenylpropylphosphine, diphenyl(p-tolyl)phosphine,diphenyl(trimethylsilyl)phosphine, diphenylvinylphosphine,divinylphenylphosphine, ethyldiphenylphosphine,(2-methoxyphenyl)methylphenylphosphine, tri-n-octylphosphine,tris(3,5-bis(trifluoromethyl)phenyl)phosphine,tris(3-chlorophenyl)phosphine, tris(4-chlorophenyl)phosphine,tris(2,6-dimethoxyphenyl)phosphine, tris(3-fluorophenyl)phosphine,tris(2-furyl)phosphine, tris(2-methoxyphenyl)phosphine,tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine ,tris(3-methoxypropyl)phosphine, tris(2-thienyl)phosphine,tris(2,4,6-trimethylphenyl)phosphine, tris(trimethylsilyl)phosphine,isopropyldiphenylphosphine, dicyclohexylphenylphosphine,(+)-neomenthyldiphenylphosphine, tribenzylphosphine,diphenyl(2-methoxyphenyl)phosphine,diphenyl(pentafluorophenyl)phosphine,bis(pentafluorophenyl)phenylphosphine, andtris(pentafluorophenyl)phosphine.

Exemplary bidentate phosphine ligands include but are not limitedto(R)-(+)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthy;bis(dicyclohexylphosphino)methane; bis(dicyclohexylphosphino)ethane;bis(diphenylphosphino)methane; bis(diphenylphosphino)ethane.

The phosphine ligands can also be selected from phosphine compounds thatare water soluble thereby imparting the resulting catalysts withsolubility in aqueous media. Selected phosphines of this type includebut are not limited to carboxylic substituted phosphines such as4-(diphenylphosphine)benzoic acid, and 2-(diphenylphosphine)benzoicacid, sodium 2-(dicyclohexylphosphino)ethanesulfonate,4,4′-(phenylphosphinidene)bis(benzene sulfonic acid) dipotassium salt,3,3′,3″-phosphinidynetris(benzene sulfonic acid) trisodium salt,4-(dicyclohexylphosphino)-1,1-dimethylpiperidinium chloride,4-(dicyclohexylphosphino)-1,1-dimethylpiperidinium iodide, quaternaryamine-functionalized salts of phosphines such as2-(dicyclohexylphosphino)-N,N,N-trimethylethanaminium chloride,2,2′-(cyclohexylphosphinidene)bis[N,N,N-trimethylethanaminiumdichloride,2,2′-(cyclohexylphosphinidene)bis(N,N,N-trimethylethanaminium) diiodide,and 2-(dicyclohexylphosphino)-N,N,N-trimethylethanaminium iodide.

Examples of phosphite ligands include but are not limited totrimethylphosphite, diethylphenylphosphite, triethylphosphite,tris(2,4-di-t-butylphenyl)phosphite, tri-n-propylphosphite,triisopropylphosphite, tri-n-butylphosphite, tri-sec-butylphosphite,triisobutylphosphite, tri-t-butylphosphite, dicyclohexylphosphite,tricyclohexylphosphite, triphenylphosphite, tri-p-tolylphosphite,tris(p-trifluoromethylphenyl)phosphite, benzyldiethylphosphite, andtribenzylphosphite.

Examples of phosphinite ligands include but are not limited to methyldiphenylphosphinite, ethyl diphenylphosphinite, isopropyldiphenylphosphinite, and phenyl diphenylphosphinite.

Examples of phosphonite ligands include but are not limited to diphenylphenylphosphonite, dimethyl phenylphosphonite, diethylmethylphosphonite, diisopropyl phenylphosphonite, and diethylphenylphosphonite.

Representative labile neutral electron donor ligands (L″) are reactiondiluent, reaction monomers, DMF, DMSO, dienes including C₄ to C₁₀aliphatic and C₄ to C₁₀ cycloaliphatic dienes representative dienesinclude butadiene, 1,6-hexadiene, and cyclooctadiene (COD), water,chlorinated alkanes, alcohols, ethers, ketones, nitrites, arenes,phosphine oxides, organic carbonates and esters.

Representative chlorinated alkanes include but are not limited todichloromethane, 1,2-dichloroethane, and carbon tetrachloride.

Suitable alcohol ligands can be selected from alcohols of the formulaR^(9′)OH, wherein R^(9′) represents linear and branched C₁-C₂₀ alkyl,linear and branched C₁-C₂₀ haloalkyl, substituted and unsubstitutedC₃-C₂₀ cycloalkyl, substituted and unsubstituted C₆-C₁₈ aryl, andsubstituted and unsubstituted C₆-C₁₈ aralkyl. When substituted, thecycloalkyl, aryl and aralkyl groups can be monosubstituted ormultisubstituted, wherein the substituents are independently selectedfrom hydrogen, linear and branched C₁-C₁₂ alkyl, linear and branchedC₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, C₆-C₁₂ aryl, andhalogen selected from chlorine, bromine, and fluorine. Representativealcohols include but are not limited to methanol, ethanol, n-propanol,isopropanol, butanol, hexanol, t-butanol, neopentanol, phenol,2,6-di-i-propylphenol, 4-t-octylphenol, 5-norbornene-2-methanol, anddodecanol.

Suitable ether ligands and thioether ligands can be selected from ethersand thioethers of the formulae (R^( ′)—O—R^(10′)) and(R^(10′)—S—R^(10′)), respectively, wherein R¹⁰ independently representslinear and branched C₁-C₁₀ alkyl radicals, linear and branched C₁-C₂₀haloalkyl, substituted and unsubstituted C₃-C₂₀ cycloalkyl, linear andbranched C₁-C₂₀ alkoxy substituted and unsubstituted C₆-C₁₈ aryl, andsubstituted and unsubstituted C₆-C₁₈ aralkyl. When substituted, thecycloalkyl, aryl and aralkyl groups can be monosubstituted ormultisubstituted, wherein the substituents are independently selectedfrom hydrogen, linear and branched C₁-C₁₂ alkyl, linear and branchedC₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, C₆-C₁₂ aryl, andhalogen selected from chlorine, bromine, and fluorine. taken togetheralong with the oxygen or sulfur atom to which they are attached to forma cyclic ether or cyclic thioether. Representative ethers include butare not limited to dimethyl ether, dibutyl ether, methyl-t-butyl ether,di-i-propyl ether, diethyl ether, dioctyl ether, 1,4-dimethoxyethane,THF, 1,4-dioxane and tetrahydrothiophene.

Suitable ketone ligands are represented by ketones of the formulaR^(11′)C(O)R^(11′) wherein R^(11′) independently represents hydrogen,linear and branched C₁-C₂₀ alkyl, linear and branched C₁-C₂₀ haloalkyl,substituted and unsubstituted C₃-C₂₀ cycloalkyl, substituted andunsubstituted C₆-C₁₈ aryl, and substituted and unsubstituted C₆-C₁₈aralkyl. When substituted, the cycloalkyl, aryl and aralkyl groups canbe monosubstituted or multisubstituted, wherein the substituents areindependently selected from hydrogen, linear and branched C₁-C₁₂ alkyl,linear and branched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy,C₆-C₁₂ aryl, and halogen selected from chlorine, bromine, and fluorine.Representative ketones include but are not limited to acetone, methylethyl ketone, cyclohexanone, and benzophenone.

The nitrile ligands can be represented by the formula R^(12′)CN, whereinR^(12′) represents hydrogen, linear and branched C₁-C₂₀ alkyl, linearand branched C₁-C₂₀ haloalkyl, substituted and unsubstituted C₃-C₂₀cycloalkyl, substituted and unsubstituted C₆-C₁₈ aryl, and substitutedand unsubstituted C₆-C₁₈ aralkyl. When substituted, the cycloalkyl, aryland aralkyl groups can be monosubstituted or multisubstituted, whereinthe substituents are independently selected from hydrogen, linear andbranched C₁-C₁₂ alkyl, linear and branched C₁-C₅ haloalkyl, linear andbranched C₁-C₅ alkoxy, C₆-C₁₂ aryl, and halogen selected from chlorine,bromine, and fluorine. Representative nitrites include but are notlimited to acetonitrile, propionitrile, benzonitrile, benzyl cyanide,and 5-norbornene-2-carbonitrile.

The arene ligands can be selected from substituted and unsubstitutedC₆-C₁₂ arenes containing monosubstitution or multisubstitution, whereinthe substituents are independently selected from hydrogen, linear andbranched C₁-C₁₂ alkyl, linear and branched C₁-C₅ haloalkyl, linear andbranched C₁-C₅ alkoxy, C₆-C₁₂ aryl, and halogen selected from chlorine,bromine, and fluorine. Representative arenes include but are not limitedto toluene, benzene, o-, m-, and p-xylenes, mesitylene, fluorobenzene,o-difluorobenzene, p-difluorobenzene, chlorobenzene, pentafluorobenzene,o-dichlorobenzene, and hexafluorobenzene.

Suitable trialkyl and triaryl phosphine oxide ligands can be representedby phosphine oxides of the formula P(O)(R^(13′))₃, wherein R^(13′)independently represents linear and branched C₁-C₂₀ alkyl, linear andbranched C₁-C₂₀ haloalkyl, substituted and unsubstituted C₃-C₂₀cycloalkyl, linear and branched C₁-C₂₀ alkoxy, linear and branchedC₁-C₂₀ haloalkoxy, substituted and unsubstituted C₆-C₁₈ aryl, andsubstituted and unsubstituted C₆-C₁₈ aralkyl. When substituted, thecycloalkyl, aryl and aralkyl groups can be monosubstituted ormultisubstituted, wherein the substituents are independently selectedfrom hydrogen, linear and branched C₁-C₁₂ alkyl, linear and branchedC₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, C₆-C₁₂ aryl, andhalogen selected from chlorine, bromine, and fluorine. Representativephosphine oxides include but are not limited to triphenylphosphineoxide, tributylphosphine oxide, trioctylphosphine oxide,tributylphosphate, and tris(2-ethylhexyl)phosphate.

Representative carbonates include but are not limited to ethylenecarbonate and propylene carbonate.

Representative esters include but are not limited to ethyl acetate andi-amyl acetate.

WCA Description

The weakly coordinating counteranion complex, [WCA], of Formula I can beselected from borates and aluminates, boratobenzene anions, carboraneand halocarborane anions.

The borate and aluminate weakly coordinating counteranions arerepresented by Formulae II and III below:

[M′(R^(24′))(R^(25′)) (R^(26′))(R^(27′))]⁻  II

[M′(OR^(28′))(OR^(29′)) (OR^(30′))(OR^(31′))]⁻  III

wherein in Formula II M′ is boron or aluminum and R^(24′), R^(25′),R^(26′), and R^(27′) independently represent fluorine, linear andbranched C₁-C₁₀ alkyl, linear and branched C₁-C₁₀ alkoxy, linear andbranched C₃-C₅ haloalkenyl, linear and branched C₃-C₁₂ trialkylsiloxy,C₁₈-C₃₆ triarylsiloxy, substituted and unsubstituted C₆-C₃₀ aryl, andsubstituted and unsubstituted C₆-C₃₀ aryloxy groups wherein R^(24′) toR^(27′) can not all simultaneously represent alkoxy or aryloxy groups.When substituted the aryl groups can be monosubstituted ormultisubstituted, wherein the substituents are independently selectedfrom linear and branched C₁-C₅ alkyl, linear and branched C₁-C₅haloalkyl, linear and branched C₁-C₅ alkoxy, linear and branched C₁-C₅haloalkoxy, linear and branched C₁-C₁₂ trialkylsilyl, C₆-C₁₈triarylsilyl, and halogen selected from chlorine, bromine, and fluorine,preferably fluorine. Representative borate anions under Formula IIinclude but are not limited to tetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-i-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,(triphenylsiloxy)tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate,tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate.

Representative aluminate anions under Formula II include but are notlimited to tetrakis(pentafluorophenyl)aluminate,tris(perfluorobiphenyl)fluoroaluminate,(octyloxy)tris(pentafluorophenyl)aluminate,tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, andmethyltris(pentafluorophenyl)aluminate.

In Formula III M′ is boron or aluminum, R^(28′), R^(29′), R^(30′), andR^(31′) independently represent linear and branched C₁-C₁₀ alkyl, linearand branched C₁-C₁₀ haloalkyl, C₂-C₁₀ haloalkenyl, substituted andunsubstituted C₆-C₃₀ aryl, and substituted and unsubstituted C₇-C₃₀aralkyl groups, subject to the proviso that at least three of R^(28′) toR^(31′) must contain a halogen containing substituent. When substitutedthe aryl and aralkyl groups can be monosubstituted or multisubstituted,wherein the substituents are independently selected from linear andbranched C₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl, linear andbranched C₁-C₅ alkoxy, linear and branched C₁-C₁₀ haloalkoxy, andhalogen selected from chlorine, bromine, and fluorine, preferablyfluorine. The groups OR^(28′) and OR^(29′) can be taken together to forma chelating substituent represented by —O—R^(32′)—O—, wherein the oxygenatoms are bonded to M′ and R^(32′) is a divalent radical selected fromsubstituted and unsubstituted C₆-C₃₀ aryl and substituted andunsubstituted C₇-C₃₀ aralkyl. Preferably, the oxygen atoms are bonded,either directly or through an alkyl group, to the aromatic ring in theortho or meta position. When substituted the aryl and aralkyl groups canbe monosubstituted or multisubstituted, wherein the substituents areindependently selected from linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, linear andbranched C₁-C₁₀ haloalkoxy, and halogen selected from chlorine, bromine,and fluorine, preferably fluorine. Representative structures of divalentR^(32′) radicals are illustrated below:

wherein R^(33′) independently represents hydrogen, linear and branchedC₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl, and halogen selectedfrom chlorine, bromine, and fluorine, preferably fluorine; R^(34′) canbe a monosubstituent or taken up to four times about each aromatic ringdepending on the available valence on each ring carbon atom andindependently represents hydrogen, linear and branched C₁-C₅ alkyl,linear and branched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy,linear and branched C₁-C₁₀ haloalkoxy, and halogen selected fromchlorine, bromine, and fluorine, preferably fluorine; and n″independently represents an integer from 0 to 6. It should be recognizedthat when n″ is 0 the oxygen atom in the formula —O—R^(32′)—O— is bondeddirectly to a carbon atom in the aromatic ring represented by R^(32′).In the above divalent structural formulae the oxygen atom(s), i.e., whenn″ is 0, and the methylene or substituted methylene group(s),—(C(R^(33′))₂)_(n″)—, are preferably located on the aromatic ring in theortho or meta positions. Representative chelating groups of the formula—O—R^(32′)—O— include but are not limited to are2,3,4,5-tetrafluorobenzenediolate (—OC₆F₄O—),2,3,4,5-tetrachlorobenzenediolate (—OC₆Cl₄O—), and2,3,4,5-tetrabromobenzenediolate (—OC₆Br₄O—), andbis(1,1′-bitetrafluorophenyl-2,2′-diolate).

Representative borate and aluminate anions under Formula III include butare not limited to [B(OC(CF₃)₃)₄]⁻, [B(OC(CF₃)₂(CH₃))₄]⁻,[B(OC(CF₃)₂H)₄]⁻, [B(OC(CF₃)(CH₃)H)₄]⁻, [Al(OC(CF₃)₂Ph)₄]⁻,[B(OCH₂(CF₃)₂)₄]⁻, [Al(OC(CF₃)₂C₆H₄CH₃)₄]⁻, [Al(OC(CF₃)₃)₄]⁻,[Al(OC(CF₃)(CH₃)H)₄]⁻, [Al(OC(CF₃)₂H)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]⁻,[Al(OC(CF₃)₂C₆H₄-4-t-butyl)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄,]⁻,[Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,]⁻,[Al(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-si-i-Pr₃)₄]⁻,[Al(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄]⁻, [Al(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄]⁻, and[Al(OC(CF₃)₂C₆F₅)₄]⁻.

The boratobenzene anions useful as the weakly coordinating counteranioncan be represented by Formula IV below:

wherein R^(34′) is selected from fluorine, fluorinated hydrocarbyl,perfluorocarbyl, and fluorinated and perfluorinated ethers. As used hereand throughout the specification, the term halohydrocarbyl means that atleast one hydrogen atom on the hydrocarbyl radical, e.g., alkyl,alkenyl, alkynyl, cycloalkyl, aryl, and aralkyl groups, is replaced witha halogen atom selected from chlorine, bromine, iodine, and fluorine(e.g., haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, haloaryl,and haloaralkyl). The term fluorohydrocarbyl means that at least onehydrogen atom on the hydrocarbyl radical is replaced by fluorine. Thedegree of halogenation can range from at least one hydrogen atom being-replaced by a halogen atom (e.g., a monofluoromethyl group) to fullhalogenation (perhalogenation) wherein all hydrogen atoms on thehydrocarbyl group have been replaced by a halogen atom (e.g.,perhalocarbyl such as trifluoromethyl (perfluoromethyl)). Thefluorinated hydrocarbyl and perfluorocarbyl radicals preferably contain1 to 24 carbon atoms, more preferably, 1 to 12 carbon atoms and mostpreferably 6 carbon atoms and can be linear or branched, cyclic, oraromatic. The fluorinated hydrocarbyl and perfluorocarbyl radicalsinclude but are not limited to fluorinated and perfluorinated linear andbranched C₁-C₂₄ alkyl, fluorinated and perfluorinated C₃-C₂₄ cycloalkyl,fluorinated and perfluorinated C₂-C₂₄ alkenyl, fluorinated andperfluorinated C₃-C₂₄ cycloalkenyl, fluorinated and perfluorinatedC₆-C₂₄ aryl, and fluorinated and perfluorinated C₇-C₂₄ aralkyl. Thefluorinated and perfluorocarbyl ether substituents are represented bythe formulae —(CH₂)_(m)OR^(36′), or —(CF₂)_(m)OR^(36′) respectively,wherein R^(36′) is a fluorinated or perfluorocarbyl group as definedabove, m is and integer of 0 to 5. It is to be noted that when m is 0the oxygen atom in the ether moiety is directly bonded attached to theboron atom in the boratobenzene ring.

Preferred R^(34′) radicals include those that are electron withdrawingin nature such as, for example, fluorinated and perfluorinatedhydrocarbyl radicals selected from trifluoromethyl, perfluoroethyl,perfluoropropyl, perfluoroisopropyl, pentafluorophenyl andbis(3,5-trifluoromethyl)phenyl.

R^(35′) independently represents hydrogen, halogen, perfluorocarbyl, andsilylperfluorocarbyl radicals, wherein the perfluorocarbyl andsilylperfluorocarbyl are as defined previously. Preferred halogen groupsare selected from chlorine, fluorine, with fluorine being especiallypreferred. When R^(35′) is halogen, perfluorocarbyl, and/orsilylperfluorocarbyl, the radical(s) are preferably ortho or para (morepreferably para) to the boron atom in the boratobenzene ring.

Representative boratobenzene anions include but are not limited to[1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-borate,4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borate,1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borate, and1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borate.

The carborane and halocarborane anions useful as the weakly coordinatingcounteranion include but are not limited to CB₁₁(CH₃)₁₂ ⁻, CB₁₁H₁₂ ⁻,1-C₂H₅CB₁₁H₁₁ ₃₁ , 1-Ph₃SiCB₁₁H₁₁ ⁻, 1-CF₃CB₁₁H₁₁ ⁻, 12-BrCB₁₁H₁₁ ⁻,12-BrCB₁₁H₁₁ ⁻, 7,12-Br₂CB₁₁H₁₀ ⁻, 12-ClCB₁₁H₁₁ ⁻, 7,12-Cl₂CB₁₁H₁₀ ⁻,1-H-CB₁₁F₁₁ ⁻, 1-CH₃-CB₁₁F₁₁ ⁻, 1-CF₃-CB₁₁F₁₁ ⁻, 12-CB₁₁H₁₁F⁻,7,12-CB₁₁H₁₁F₁₂ ⁻, 7,9,12-CB₁₁H₁₁F₃ ⁻, CB₁₁H₆Br₆ ⁻, 6-CB₉H₉F⁻,6,8-CB₉H₈F₂ ⁻, 6,7,8-CB₉H₇F₃ ⁻, 6,7,8,9-CB₉H₆F₄ ⁻, 2,6,7,8,9-CB₉H₅F₅ ⁻,CB₉H₅Br₅ ⁻, CB₁₁H₆Cl₆ ⁻, CB₁₁H₆F₆ ⁻, CB₁₁H₆F₆ ⁻, CB₁₁H₆I₆ ⁻, CB₁₁H₆Br₆⁻, 6,7,9,10,11,12-CB₁₁H₆F₆ ⁻, 2,6,7,8,9,10-CB₉H₅F₅ ⁻, 1-H-CB₉F₉ ⁻,12-CB₁₁H₁₁(C₆H₅)⁻, 1-C₆F₅-CB₁₁H₅Br₆ ⁻, CB₁₁Me₁₂ ⁻, CB₁₁(CF₃)₁₂ ⁻,Co(B₉C₂H₁₁)₂ ⁻, CB₁₁(CH₃)₁₂ ⁻, CB₁₁(C₄H₉)₁₂ ⁻, CB₁₁(C₆H₁₃)₁₂ ⁻,Co(C₂B₉H₁₁)₂ ⁻, Co(Br₃C₂B₉H₈)₂ ⁻ and dodecahydro-1-carbadodecaborate.

Catalyst Preparation

The catalysts of Formula I can be prepared as a preformed singlecomponent catalyst in solvent or can be prepared in situ by admixing thecatalyst precursor components in the desired monomer to be polymerized.

The single component catalyst of Formula I can be prepared by admixingthe catalyst precursors in an appropriate solvent, allowing the reactionto proceed under appropriate temperature conditions, and isolating thecatalyst product. In another embodiment, a Group 10 metal procatalyst isadmixed with a Group 15 electron donor compound and/or a labile neutralelectron donor compound, and a salt of a weakly coordinating anion in anappropriate solvent to yield the preformed catalyst complex set forthunder Formula I above. In another embodiment a Group 10 metalprocatalyst containing a Group 15 electron donor ligand is admixed witha salt of a weakly coordinating anion in an appropriate solvent to yieldthe preformed catalyst complex.

The catalyst preparation reactions are carried out in solvents that areinert under the reaction conditions. Examples of solvents suitable forthe catalyst preparation reaction include but are not limited to alkaneand cycloalkane solvents such as pentane, hexane, heptane, andcyclohexane; halogenated alkane solvents such as dichloromethane,chloroform, carbon tetrachloride, ethylchloride, 1,1-dichloroethane,1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane,2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; etherssuch as THF and diethylether; aromatic solvents such as benzene, xylene,toluene, mesitylene, chlorobenzene, and o-dichlorobenzene; andhalocarbon solvents such as Freon® 112; and mixtures thereof. Preferredsolvents include benzene, fluorobenzene, o-difluorobenzene,p-difluorobenzene, pentafluorobenzene, hexafluorobenzene,o-dichlorobenzene, chlorobenzene, toluene, o-, m-, and p-xylenes,mesitylene, cyclohexane, THF, and dichloromethane.

A suitable temperature range for carrying out the reaction is from about−80° C. to about 150° C., preferably from about −30° C. to about 100°C., more preferably from about 0° C. to about 65° C., and mostpreferably from about 10° C. to about 40° C. Pressure is not criticalbut may depend on the boiling point of the solvent employed, i.e.sufficient pressure to maintain the solvent in the liquid phase.Reaction times are not critical, and can range from several minutes to48 hours. The reactions are preferably carried out under inertatmosphere such as nitrogen or argon.

The reaction is carried out by dissolving the procatalyst in a suitablesolvent and admixing the appropriate ligand(s) and the salt of thedesired weakly coordinating anion with the dissolved procatalyst, andoptionally heating the solution until the reaction is complete. Thepreformed single component catalyst can be isolated or can be useddirectly by adding aliquots of the preformed catalyst in solution to thepolymerization medium. Isolation of the product can be accomplished bystandard procedures, such as evaporating the solvent, washing the solidwith an appropriate solvent, and then recrystallizing the desiredproduct. The molar ratios of catalyst components employed in thepreparation the preformed single component catalyst of the invention isbased on the metal contained in the procatalyst component. In apreferred embodiment the molar ratio of procatalyst/Group 15 electrondonor component/WCA salt is 1:1-10:1-100, more preferably, 1:1-5:1-20,and most preferably, 1:1-2:1-5. In embodiments of the invention wherethe procatalyst is ligated with a Group 15 electron donor ligand and/ora labile neutral electron donor ligand the molar ratio of procatalyst(based on the metal content) to WCA salt 1:1-100, preferably, 1:1-20,and more preferably, 1:1-5.

In one embodiment, a Group 10 metal procatalyst dimer of the formula[R′MA′]₂ is admixed with a Group 15 electron donor compound, (L′), and asalt of a suitable weakly coordinating anion in an appropriate solventto produce the single component catalyst product as shown in equation(1) below.

[R′MA′]₂+xL′+yL″+[WCA] salt→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  1.

Suitable procatalyst dimers of the formula [R′MA′]₂ include but are notlimited to the following compositions (allyl)palladiumtrifluoroacetatedimer, (allyl)palladiumchloride dimer, (crotyl)palladiumchloride dimer,(allyl)palladiumiodide dimer, (β-pinenyl)palladiumchloride dimer,methallylpalladium chloride dimer, 1,1-dimethylallylpalladium chloridedimer, and (allyl)palladiumacetate dimer.

In another embodiment, a ligated Group 10 metal procatalyst of theformula [R′M(L″)_(y)A′] is admixed with a Group 15 electron donorcompound, (L′), and a salt of a suitable weakly coordinating anion in anappropriate solvent to produce the single component catalyst product asshown in equation (2) below.

[R′M(L″)_(y)A′]+xL′+[WCA] salt→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  2.

A representative procatalyst of the formula [R′M(L″)_(y)A′] includes butis not limited to (COD)palladium (methyl)chloride.

In a further embodiment, a Group 10 metal ligated procatalyst of theformula [R′M(L″)_(x)A′] containing the Group 15 electron donor ligand(L′) is admixed with a salt of a suitable weakly coordinating anion inan appropriate solvent to produce the single component catalyst productas shown in equation (3) below.

[R′M(L′)_(x)A′]+yL″+[WCA] salt→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  3.

Suitable procatalysts of the formula [R′M(L″)_(x)A′] include but are notlimited to the following compositions:(allyl)palladium(tricyclohexylphosphine)chloride,(allyl)palladium(tricyclohexylphosphine)triflate,(allyl)palladium(triisopropylphosphine)triflate,(allyl)palladium(tricyclopentylphosphine)triflate, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate,(allyl)palladium(tri-o-tolylphosphine)chloride,(allyl)palladium(tri-o-tolylphosphine)triflate,(allyl)palladium(tri-o-tolylphosphine)nitrate,(allyl)palladium(tri-o-tolylphosphine)acetate, (allyl)palladium(triisopropylphosphine)triflimide,(allyl)palladium(tricyclohexylphosphine)triflimide,(allyl)palladium(triphenylphosphine)triflimide,(allyl)palladium(trinaphthylphosphine)triflate,(allyl)palladium(tricyclohexylphosphine) p-tolylsulfonate,(allyl)palladium(triphenylphosphine)triflate,(allyl)palladium(triisopropylphosphine)trifluoroacetate,(allyl)platinum(tricyclohexylphosphine)chloride,(allyl)platinum(tricyclohexylphosphine)triflate,(1,1-dimethylallyl)palladium(triisopropylphosphine)trifluoroacetate.(2-chloroallyl)palladium(triisopropylphosphine)trifluoroacetate,(crotyl)palladium(triisopropylphosphine)triflate,(crotyl)palladium(tricyclohexylphosphine)triflate,(crotyl)palladium(tricyclopentylphosphine)triflate,(methallyl)palladium(tricyclohexylphosphine)triflate,(methallyl)palladium(triisopropylphosphine)triflate,(methallyl)palladium(tricyclopentylphosphine)triflate,(methallyl)palladium(tricyclohexylphosphine)chloride,(methallyl)palladium(triisopropylphosphine)chloride,(methallyl)palladium(tricyclopentylphosphine)chloride,(methallyl)palladium(tricyclohexylphosphine)triflimide,(methallyl)palladium(triisopropylphosphine)triflimide,(methallyl)palladium(tricyclopentylphosphine)triflimide,(methallyl)palladium(tricyclohexylphosphine)trifluoroaetate,(methallyl)palladium(triisopropylphosphine)trifluoroacetate,(methallyl)palladium(tricyclopentylphosphine)trifluoroacetate,(methallyl)palladium(tricyclohexylphosphine) acetate,(methallyl)palladium(triisopropylphosphine)acetate,(methallyl)palladium(tricyclopentylphosphine)acetate,(methallyl)nickel(tricyclohexylphosphine)triflate,{2-[(dimethylamino)methyl]phenyl-C,N-}-palladium(tricyclohexylphosphine)chloride,[(dimethylamino)methyl]phenyl-C,N-}-palladium(tricyclohexylphosphine)triflate,(hydrido)palladium bis(tricyclohexylphosphine)triflate,(hydrido)palladium bis(tricyclohexylphosphine)fonrmate(hydrido)palladium bis(tricyclohexylphosphine)chloride,(hydrido)palladium bis(triisopropylphosphine)chloride,(hydrido)palladium bis(tricyclohexylphosphine)nitrate,(hydrido)palladium bis(tricyclohexylphosphine)trifluoroacetate, and(hydrido)palladium bis(triisopropylphosphine)triflate.

Other procatalyst components suitable for use in the foregoing processinclude (Me₂NCH₂C₆H₄)Pd(O₃SCF₃)P(cyclohexyl)₃ (i.e.,ortho-metallatedphenylmethlyenedimethylamino palladiumtricyclohexylphosphine), (allyl)Pd(P-i-Pr₃)C₆F₅, (allyl)Pd(PCy₃)C₆F₅,(CH₃)Pd(PMe₃)₂Cl, (C₂H₅)Pd(PMe₃)₂Cl (Ph)Pd(PMe₃)₂Cl, (CH₃)Pd(PMe₃)₂Br,(CH₃)Pd(PMe₂Ph)₂Cl, (C₂H₅)Pd(PMe₃)₂Br, (C₂H₅)Pd(PMe₃)₂Br,(Ph)Pd(PMe₃)₂Br, (CH₃)Pd(PMe₃)NO₃, (CH₃)Pd(P(i-Pr)₃)₂O₃SCCF₃,(π¹-benzyl)Pd(PEt₃)₂Cl, (allyl)Pd(PMe₃)OC(O)CH₂CH═CH₂,(allyl)Pd(AsPh₃)Cl, (allyl)Pd(PPh₃)Cl, (allyl)Pd(SbPh₃)Cl,(methylallyl)Pd(PPh₃)Cl, (methylallyl)Pd(AsPh₃)Cl,(methylallyl)Pd(SbPh₃)Cl, (methylallyl)Pd(PBu₃)Cl, and(methylallyl)Pd(P[(OCH₂)₃]CH)Cl.

In another embodiment, the catalyst can be formed by protonating aprocatalyst of the formula:

in the presence of a Brønsted acid based WCA salt or an equivalentreaction utilizing a carbonium or silylium based WCA salt to yield anactive catalyst as illustrated in Eq. 4.

In this embodiment R′ is a divalent hydrocarbyl ligand of the formula—(C_(d)H_(2d))— that is taken together with the Group 10 metal center Mto form a metallacycle where d′ represents the number of carbon atoms inthe divalent hydrocarbyl backbone and is an integer from 3 to 10. Any ofthe hydrogen atoms on the divalent hydrocarbyl backbone can be replacedby linear and branched C₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl,C₅-C₁₀ cycloalkyl, and C₆-C₁₀ aryl. The cycloalkyl and aryl moieties canoptionally be substituted with a halogen substituent selected frombromine, chlorine, fluorine, and iodine, preferably fluorine. Inaddition, any two or three of the alkyl substituents taken together withthe hydrocarbyl backbone carbon atoms to which they are attached canform an aliphatic or aromatic ring system. The rings can be monocyclic,polycyclic, or fused. Protonation occurs at one of the hydrocarbyl/metalcenter bond interfaces to yield a cation complex with a monovalenthydrocarbyl ligand coordinated to the metal center M.

In another embodiment a Group 10 metal ligated procatalyst of theformula [R′M(L′)_(x)(L′)_(y)A′] containing a Group 15 electron donorligand (L′) and a labile neutral electron donor ligand (L″) is admixedwith a salt of a suitable weakly coordinating anion in an appropriatesolvent to produce the single component catalyst product as shown inequation (5) below.

[R′M(L′)_(x)(L″)_(y)A′]+[WCA]salt→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  5.

Suitable procatalysts of the formula [R′M(L′)_(x)(L″)_(y)A′] include butare not limited to the following compositions:[(allyl)Pd(NCCH₃)(P-i-Pr₃)][B(O₂-3,4,5,6-Cl₄C₆)₂],[(allyl)Pd(HOCH₃)(P-i-Pr₃)][B(O₂-3,4,5,6-Cl₄C₆)₂],[(allyl)Pd(HOCH₃)(P-i-Pr₃)][B(O₂-3,4,5,6-Br₄C₆)₂],[(allyl)Pd(HOCH₃)(P-i-Pr₃)][B(O₂C₆H₄)₂],[(allyl)Pd(OEt₂)(P-i-Pr₃)][BPh₄], [(allyl)Pd(OEt₂)(P-i-Pr₃)],[SbF₆][(allyl)Pd(OEt₂)(P-i-Pr₃)][BF₄], [(allyl)Pd(OEt₂)(PCy₃)][BF₄],[(allyl)Pd(OEt₂)(PPh₃)][BF₄], [(allyl)Pd(OEt₂)(P-i-Pr₃)][PF₆],[(allyl)Pd(OEt₂)(PCy₃)][PF₆], [(allyl)Pd(OEt₂)(PPh₃)][PF₆],[(allyl)Pd(OEt₂)(P-i-Pr₃)][ClO₄], [(allyl)Pd(OEt₂)(PCy₃)][ClO₄],[(allyl)Pd(OEt₂)(PPh₃)][ClO₄], [(allyl)Pd(OEt₂)(P-i-Pr₃)][SbF₆],[(allyl)Pd(OEt₂)(PCy₃)][SbF₆], and [(allyl)Pd(OEt₂)(PPh₃)][SbF₆].

In another embodiment of the invention the catalyst of Formula I isgenerated by reacting a procatalyst of the formula[M(L′)_(x)(L″)_(y)(A′)₂] with an organometallic compound of aluminum,lithium or magnesium, and a source of a weakly coordinating anion (WCA)or a strong Lewis Acid. In this embodiment the anionic hydrocarbylligand (R′) on the group 10 metal center (M) is supplied via reactionwith the organometallic compound to yield the active catalyst as shownbelow.

[M(L′)_(x)(L″)_(y)(A′)₂]+[WCA] salt or Strong Lewis Acid+organometalliccompound→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  6.

Examples of procatalysts suitable for use in this embodiment include:

nickel acetylacetonate,

nickel carboxylates,

nickel (II) chloride,

nickel (II) bromide,

nickel ethylhexanoate,

nickel (II) trifluoroacetate,

nickel (II) hexafluoroacetylacetonate,

NiCl₂(PPh₃)₂,

NiBr₂(P(p-tolyl)₃)₂,

trans-PdCl₂(PPh₃)₂,

palladium (II) bis(trifluoroacetate),

palladium (II) acetylacetonate,

(cyclooctadiene)palladium (II) dichloride,

Pd(acetate)₂(PPh₃)₂,

PdC₂(PPh₃)₂

PdBr₂(PPh₃)₂

PdBr₂(P(P-tolyl)₃)₂,

PdCl₂(P(o-tolyl)₃)₂,

PdCl₂(P(cyclohexyl)₃)₂,

palladium (II) bromide,

palladium (II) chloride,

palladium (II) iodide,

palladium (II) ethylhexanoate,

dichloro bis(acetonitrile)palladium (II),

dibromo bis(benzonitrile)palladium (II),

platinum (II) chloride,

platinum (II) bromide, and

platinum bis(triphenylphosphine)dichloride.

In general the Group 10 metal procatalyst is a nickel (II), platinum(II) or palladium (II) compound containing two anionic leaving groups(A′), which can be readily displaced by the weakly coordinating anionthat is provided by the WCA salt or strong Lewis acid described belowand can be replaced by hydrocarbyl groups originating from theorganometallic compound. The leaving groups can be the same ordifferent. The Group 10 metal procatalyst may or may not be ligated.

When the procatalyst of this embodiment is not ligated with a Group 15electron donor component (L′), the Group 15 electron donor ligand can beadded to the reaction medium as shown in the following reaction scheme.

 [M(L″)_(y)(A′)₂]+xL′+[WCA] salt or Strong Lewis Acid+organometalliccompound →[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  7.

The strong Lewis acids suitable for use in this embodiment are selectedfrom compounds of the formula:

M′(R^(41′))₃

wherein M′ represents aluminum or boron and R^(41′) representsmonosubstituted and multisubstituted C₆-C₃₀ aryl, wherein thesubstituents on the aryl group are independently selected from halogen,preferably fluorine, linear and branched C₁-C₅ haloalkyl, preferablytrifluoromethyl, and halogenated and perhalogenated phenyl, preferablypentafluorophenyl. Examples of such strong Lewis acids include:tris(pentafluorophenyl)boron, tris(3,5-bis(trifluoromethyl)phenyl)boron,tris(2,2′,2″-nonafluorobiphenyl)borane, andtris(pentafluorophenyl)aluminum.

The organometallic compound is a hydrocarbyl derivative of silicon,germanium, tin, lithium, magnesium or aluminum. Aluminum derivatives arepreferred. The organoaluminum component of the catalyst system isrepresented by the formula:

AIR′_(3−x″)Q_(x″)

wherein R′ independently represents hydrogen, linear and branched C₁-C₂₀alkyl, C₅-C₁₀ cycloalkyl, linear and branched C₂-C₂₀ alkenyl, C₆-C₁₅cycloalkenyl, allylic ligands or canonical forms thereof, C₆-C₂₀ aryl,and C₇-C₃₀ aralkyl, *Q is a halide or pseudohalide selected fromchlorine, fluorine, bromine, iodine, linear and unbranched C₁-C₂₀alkoxy, C₆-C₂₄ aryloxy; x″ is 0 to 2.5, preferably 0 to 2, mostpreferably 0 to 1. Trialkylaluminum compounds are most preferred.Examples of suitable organometallic compounds include: methyllithium,sec-butyllithium, n-butyllithium, phenyllithium, butylethylmagnesium,di-n-butylmagnesium, butyloctylmagnesium, trimethylaluminum,triethylaluminum, tri-n-propylaluminum, tri-i-propylaluminum,tri-i-butylaluminum, tri-2-methylbutylaluminum, tri-octylaluminum,diethylaluminum chloride, ethylaluminum dichloride, di-i-butylaluminumchloride, diethylaluminum bromide, ethylaluminum sesquichloride,diethylaluminum ethoxide, diethylaluminum(i-butylphenoxide), anddiethylaluminum(2,4-di-tert-butylphenoxide).

Embodiments of the catalyst devoid of a hydrocarbyl containing ligandcan be synthesized by reacting a procatalyst of the formula [M(A′)₂]with the desired ligands and WCA salt in accordance with the followingreaction scheme:

[M(A′)₂]+xL′+2[WCA] salt→[M(L′)_(x)][WCA]₂+2A′ salt  8.

wherein x=1 or 2, M, L′, and L″ are as previously defined.

Examples of procatalyst compounds include palladium (II)bis(acetylacetonate, palladium (acetate)₂, Pd(NO₃)₂, PdCl₂, PdBr₂, andPdI₂.

The foregoing schematic equations (1 to 8) have been presented forillustrative purposes only. While they have been written in balancedform, it should be recognized that an excess of reaction components canbe employed without deviating from the spirit of invention. For example,an excess of L′, L″, A′, or WCA salt containing components can beemployed in the process of the invention so long as the process is notdeleteriously affected.

In a preferred embodiment the molar ratio of the Group 10 metal/Group 15electron donor compound/source of a weakly coordinatinganion/organometallic compound is 1:1-10:1-100:2-200, more preferably1:1-5:1-40:4-100, and most preferably 1:1-2:2-20:5-50. In embodimentswhere the Group 10 metal ion source is an adduct containing a Group 15electron donor compound, no additional Group 15 electron donor compoundneed be employed. In this embodiment the most preferred molar ratio ofthe Group 10 metal/Group 15 electron donor compound/source of a weaklycoordinating anion/organometallic compound is 1:0:2-20:5-50.

In all of the forgoing embodiments the catalysts of Formula I can beprepared as a preformed single component catalyst in solvent or they canbe prepared in situ by admixing the precursor components (ligated ornon-ligated Group 10 metal component with leaving group(s), ligandcomponent(s), and WCA source or strong Lewis acid source) in the desiredmonomer, monomer mixtures, or solutions thereof. It is also possible toadmix two or even three of the catalyst precursor components and thenadd the mixture to the monomer or monomer solution containing theremaining catalyst precursor component(s).

In the equations and formulae set forth above and throughout thespecification, R′, M, L′, L″, [WCA], b, d, x, and y are as defined aboveunless otherwise defined, A′ is an anionic leaving group which isdefined below, [WCA] salt is a metal salt of the weakly coordinatinganion [WCA], and the abbreviations Me, Et, Pr, Bu, Cy, and Ph, as usedhere and throughout the specification refer to methyl, ethyl, propyl,butyl, cyclohexyl, and phenyl, respectively.

The foregoing Group 10 metal procatalyst components are commerciallyavailable or can be synthesized by techniques well known in the art.

As discussed above catalyst complex of Formula I can be formed in situby combining any of the Group 10 metal procatalysts with the desiredcatalyst system components in monomer. In cases where the Group 10 metalprocatalyst already contains the desired ligand groups, the procatalystis mixed in monomer along with the WCA salt or the alternativeactivators such as strong Lewis acids or Bronsted acids. The WCA salt,strong Lewis acid or Brønsted acid serves as the an activator for theprocatalyst in the presence of monomer. The in situ reactions forpreparing the catalysts of Formula I generally follow the sameconditions and reaction schemes as outlined for the preparation of thepreformed single component catalysts, the principal difference beingthat the catalysts are formed in monomer in lieu of solvent and that apolymer product is formed.

Leaving Groups

A′ represents an anionic leaving group that can be readily displaced bythe weakly coordinating anion that is provided by the WCA salt. Theleaving group forms a salt with the cation on the WCA salt. Leavinggroup A′ is selected from halogen (i.e., Br, Cl, I, and F), nitrate,triflate (trifluoromethanesulfonate), triflimide(bistrifluoromethanesulfonimide), trifluoroacetate, tosylate, AlBr₄ ⁻,AlF₄ ⁻, AlCl₄ ⁻, AlF₃O₃SCF₃ ⁻, AsCl₆ ⁻, SbCl₆ ⁻, SbF₆ ⁻, PF₆ ⁻, BF₄ ⁻,ClO₄ ⁻, HSO₄ ⁻, carboxylates, acetates, acetylacetonates, carbonates,aluminates, and borates.

In another embodiment the leaving group can be a hydrocarbyl group orhalogenated hydrocarbyl group when a Brønsted acid based WCA salt isutilized as the activator. In this embodiment the activator protonatesthe hydrocarbyl or halogenated hydrocarbyl forming a neutral moiety. Theleaving group moiety is preferably selected from the hydride, linear andbranched C₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl, C₅-C₁₀cycloalkyl, and C₆-C₁₀ aryl. The cycloalkyl and aryl moieties canoptionally be substituted with a halogen substituent selected frombromine, chlorine, fluorine, and iodine, preferably fluorine. In thisembodiment, A′ is protonated to yield the neutral moiety A′H. Methyl andpentafluorophenyl groups are representative examples of leaving groupsunder this embodiment.

Halogen leaving groups include chlorine, iodine, bromine and fluorine.The acetates include groups of the formula R³⁸′C(O)O⁻, and thecarbonates include groups of the formula R³⁸′OC(O)O⁻, wherein R³⁸′represents linear and branched C₁-C₅ alkyl, linear and branched C₁-C₅haloalkyl (preferably fluorine), linear or branched C₁-C₅ alkenyl,C₆-C₁₂ aryl, optionally monosubstituted or independentlymultisubstituted with linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, and halogen (preferably fluorine).

The aluminate and borate leaving groups can be represented by theformulae M′(R³⁹′)₄ ⁻, M′(GR³⁹′)₄ ⁻, M′(—C≡CPh)⁴⁻, or a moietyrepresented by the following structures:

wherein G is a sulfur or oxygen atom Ph represents phenyl andsubstituted phenyl as defined below, and R³⁹′ independently representslinear and branched C₁-C₁₀ alkyl, linear and branched C₁-C₁₀ chloro- orbromoalkyl, C₅-C₁₀ cycloalkyl, substituted and unsubstituted aryl,preferably, phenyl and substituted phenyl, substituted and unsubstitutedC₇-C₂₀ aralkyl, preferably, phenylalkyl and substituted phenylalkyl. Bysubstituted is meant that the aryl or phenyl groups can contain one ormore of linear and branched C₁-C₅ alkyl, linear and branched C₁-C₅haloalkyl, chlorine, and bromine substituents, and combinations thereof.

Representative aluminate groups include but are not limited totetraphenoxyaluminate, tetrakis(cyclohexanolato)aluminate,tetraethoxyaluminate, tetramethoxyaluminate,tetrakis(isopropoxy)aluminate, tetrakis(2-butanolato)aluminate,tetrapentyloxyaluminate, tetrakis(2-methyl-2-propanolato)aluminate,tetrakis(nonyloxy)aluminate, andbis(2-methoxyethanolate-O,O′)bis(2-methoxyethanolate-O′)aluminate,tetrakis(phenyl)aluminate, tetrakis(p-tolyl)aluminate,tetrakis(m-tolyl)aluminate, tetrakis(2,4-dimethylphenyl)aluminate, andtetrakis(3,5-dimethylphenyl)aluminate.

Representative borate groups include tetraphenylborate,tetrakis(4-methylphenyl)borate, tetrakis(4-chlorophenyl)borate,tetrakis(4-bromophenyl)borate, tetrakis(2-bromo-4-chlorophenyl)borate,butyltriphenylborate, tetrakis(4-methoxyphenyl)borate,tetrakis(phenylethynyl)borate, bis(1,2-benzenediolato)borate,triphenyl(phenylethynyl)borate, bis(tetrafluorobenzenediolate)borate,bis(tetrachlorobenzenediolate)borate,bis(tetrabromobenzenediolate)borate,bis(1,1′-biphenyl-2,2′-diolato)borate, tetrakis(thiophenolyl)borate,bis(3,5-di-tert-butylbenzenediolate)borate,tetrakis(2,4-dimethylphenyl)borate, tetrakis(p-tolyl)borate,tetrakis(3,5-dimethylphenyl)borate, and tetrakis(m-tolyl)borate.

In addition to the anionic leaving groups described above, A′ can alsobe selected from highly fluorinated and perfluorinated alkylsulfonyl andarylsulfonyl containing anions of the formulae (R⁴⁰′SO₂)₂CH⁻,(R⁴⁰′SO₂)₃C⁻, and (R⁴⁰′SO₂)₂N⁻, wherein R⁴⁰′ independently representslinear and branched C₁-C₂₀ highly fluorinated and perfluorinated alkyl,C₅-C₁₅ highly fluorinated and perfluorinated cycloalkyl, and highlyfluorinated and perfluorinated C₆-C₂₂ aryl. Optionally, the alkyl andcycloalkyl groups can contain a heteroatom in the chain of cyclicstructure, respectively. Preferred heteroatoms include divalent(non-peroxidic) oxygen (i.e., —O—), trivalent nitrogen, and hexavalentsulfur. Any two of R⁴⁰′ can be taken together to form a ring. When R⁴⁰′is a cycloalkyl substituent, a heterocycloalkyl substituent, or is takenwith another R⁴⁰′ group to form a ring, the ring structures preferablycontain 5 or 6 atoms, 1 or 2 of which can be heteroatoms.

In the above formulae the term highly fluorinated means that at least 50percent of the hydrogen atoms bonded to the carbon atoms in the alkyl,cycloalkyl, and aryl moieties are replaced by fluorine atoms.Preferably, at least 2 out of every 3 hydrogen atoms on the alkyl,cycloalkyl, and aryl moieties under R⁴⁰′ are replaced by fluorine. Morepreferably, at least 3 out of every 4 hydrogen atoms are replaced byfluorine, and most preferably all of the hydrogen atoms on the R⁴⁰′substituent are replaced by fluorine to give the perfluorinated moiety.In addition to or in lieu of fluorine atom substitution on the arylring(s), the aryl groups can contain linear and branched C₁-C₁₀ highlyfluorinated and perfluorinated alkyl groups, such as, for example,trifluoromethyl. In embodiments where hydrogen atoms remain on thealkyl, cycloalkyl, and aryl moieties, a portion or all of the remaininghydrogen atoms can be replaced with bromine and/or chlorine atoms.

Representative highly fluorinated and perfluorinated alkylsulfonyl andarylsulfonyl containing anions of the foregoing formulae include but arenot limited to (C₂F₅SO₂)₂N⁻, (C₄F₉SO₂)₂N⁻, (CF₃SO₂)₂N³¹ ,(CF₃SO₂)(C₄F₉SO₂)N⁻, ((CF₃)₂NC₂F₄SO₂)₂N³¹ , (C₆F₅SO₂)(CF₃SO₂)N⁻,(CF₃SO₂)(CHF₂SO₂)N⁻, (C₂F₅SO₂)(CF₃SO₂)N³¹ , (C₃F₇SO₂)₂N⁻,((CF₃)₂(F)CSO₂)₂N⁻, (C₄F₈(CF₃)₂NSO₂)₂N³¹ , (C₈F₁₇SO₂)₃C⁻, (CF₃SO₂)₃C⁻,(CF₃SO₂)₂CH⁻, (C₄F₉SO₂)₃C⁻, (CF₃SO₂)₂(C₄F₉SO₂)C⁻,((CF₃)₂NC₂F₄SO₂)C(SO₂CF₃)₂ ⁻, (3,5-bis(CF₃)C₆H₃)SO₂N(SO₂CF₃)⁻,(C₆F₅SO₂)C(SO₂CF₃)₂ ⁻, and the structures exemplified below:

Additional highly fluorinated and perfluorinated alkylsulfonyl andarylsulfonyl anions suitable as leaving groups are described in Turowskyand Seppelt, Inorganic Chemistry, 1988, 27, 2135-2137, and in U.S. Pat.Nos. 4,387,222; 4,505,997; 5,021,308; 5,072,040; 5,162,177; and5,273,840 the disclosures of which are hereby incorporated by reference.

WCA Salts

The salt of the weakly coordinating anion employed in the process of thepresent invention can be represented by the formula [C(L″)_(z)]_(b)[WCA]_(d), wherein C represents a proton (H⁺), an alkaline earth metalcation, a transition metal cation or an organic group containing cation,L″ and WCA, are as defined above, z is an integer from 0 to 8, and b″and d″ represent the number of times the cation complex and weaklycoordinating counteranion complex (WCA), respectively, are taken tobalance the electronic charge on the overall salt complex.

The alkali metal cations include Group 1 metals selected from lithium,sodium, potassium, rubidium, and cesium. The preferred Group 1 metalcations are lithium, sodium and potassium.

The alkali earth metal cations include Group 2 metals selected fromberyllium, magnesium, calcium, strontium, and barium. The preferredGroup 2 metal cations are magnesium, calcium, strontium, and barium. Thetransition metal cation is selected from zinc, silver, and thallium.

The organic group cation is selected from ammonium, phosphonium,carbonium and silylium cations, i.e., [NHR⁴¹′₃]⁺, [NR⁴¹′₄]⁺, [PHR⁴¹′₃],[PR⁴¹′₄], [R⁴¹′₃C]⁺, and [R⁴¹′₃Si]⁺, where R⁴¹′ independently representsa hydrocarbyl, silylhydrocarbyl, or perfluorocarbyl group, eachcontaining 1 to 24 carbon atoms, more preferably, from 1 to 12 carbonsarranged in a linear, branched, or ring structure. By perfluorocarbyl ismeant that all carbon bonded hydrogen atoms are replaced by a fluorineatom. Representative hydrocarbyl groups include but are not limited tolinear and branched C₁-C₂₀ alkyl, C₃-C₂₀ cycloalkyl, linear and branchedC₂ to C₂₀ alkenyl, C₃-C₂₀ cycloalkenyl, C₆-C₂₄ aryl, and C₇-C₂₄ aralkyl,and organometallic cations. The organic cations are selected fromtrityl, trimethylsilylium, triethylsilylium,tris(trimethylsilyl)silylium, tribenzylsilylium, triphenylsilylium,tricyclohexylsilylium, dimethyloctadecylsilylium, and triphenylcarbenium(i.e., trityl). In addition to the above cation complexes ferroceniumcations such as [(C₅H₅)₂Fe]⁺ and [(C₅(CH₃))₂Fe]⁺ are also useful as thecation in the WCA salts of the invention.

Examples of WCA salts having a weakly coordinating anion described underFormula II include but are not limited to lithiumtetrakis(2-fluorophenyl)borate, sodium tetrakis(2-fluorophenyl)borate,silver tetrakis(2-fluorophenyl)borate, thalliumtetrakis(2-fluorophenyl)borate, lithium tetrakis(3-fluorophenyl)borate,sodium tetrakis(3-fluorophenyl)borate, silvertetrakis(3-fluorophenyl)borate, thallium tetrakis(3-fluorophenyl)borate,ferrocenium tetrakis(3-fluorophenyl)borate, ferroceniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(4-fluorophenyl)borate, sodium tetrakis(4-fluorophenyl)borate,silver tetrakis(4-fluorophenyl)borate, thalliumtetrakis(4-fluorophenyl)borate, lithiumtetrakis(3,5-difluorophenyl)borate, sodiumtetrakis(3,5-difluorophenyl)borate, thalliumtetrakis(3,5-difluorophenyl)borate, trityltetrakis(3,5-difluorophenyl)borate, 2,6-dimethylaniliniumtetrakis(3,5-difluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium(diethyl ether)tetrakis(pentafluorophenyl)borate, lithium(diethyl ether)_(2,5)tetrakis(pentafluorophenyl)borate, lithiumtetrakis(2,3,4,5-tetrafluorophenyl)borate, lithiumtetrakis(3,4,5,6-tetrafluorophenyl)borate, lithiumtetrakis(1,2,2-trifluoroethylenyl)borate, lithiumtetrakis(3,4,5-trifluorophenyl)borate, lithiummethyltris(perfluorophenyl)borate, lithiumphenyltris(perfluorophenyl)borate, lithium tris(isopropanol)tetrakis(pentafluorophenyl)borate, lithium tetrakis(methanol)tetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, tris(toluene)silvertetrakis(pentafluorophenyl)borate, tris(xylene)silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, trityltetrakis(4-triisopropylsilyltetrafluorophenyl)borate, trityltetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, thalliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, 2,6-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate lithium(triphenylsiloxy)tris(pentafluorophenyl)borate, sodium(triphenylsiloxy)tris(pentafluorophenyl)borate, sodiumtetrakis(2,3,4,5-tetrafluorophenyl)borate, sodiumtetrakis(3,4,5,6-tetrafluorophenyl)borate, sodiumtetrakis(1,2,2-trifluoroethylenyl)borate, sodiumtetrakis(3,4,5-trifluorophenyl)borate, sodiummethyltris(perfluorophenyl)borate, sodiumphenyltris(perfluorophenyl)borate, thalliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, thalliumtetrakis(3,4,5,6-tetrafluorophenyl)borate, thalliumtetrakis(1,2,2-trifluoroethylenyl)borate, thalliumtetrakis(3,4,5-trifluorophenyl)borate, sodiummethyltris(perfluorophenyl)borate, thalliumphenyltris(perfluorophenyl)borate, trityltetrakis(2,3,4,5-tetrafluorophenyl)borate, trityltetrakis(3,4,5,6-tetrafluorophenyl)borate, trityltetrakis(1,2,2-trifluoroethylenyl)borate, trityltetrakis(3,4,5-trifluorophenyl)borate, tritylmethyltris(pentafluorophenyl)borate, tritylphenyltris(perfluorophenyl)borate, silvertetrakis[3,5-bis(trifluoromethyl)phenyl]borate, silver(toluene)tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, thalliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, lithium(hexyltris(pentafluorophenyl)borate, lithiumtriphenylsiloxytris(pentafluorophenyl)borate,lithium(octyloxy)tris(pentafluorophenyl)borate, lithiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate,sodium(octyloxy)tris(pentafluorophenyl)borate, sodiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, potassiumtetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate,potassium(octyloxy)tris(pentafluorophenyl)borate, potassiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, magnesiumtetrakis(pentafluorophenyl)borate, magnesiummagnesium(octyloxy)tris(pentafluorophenyl)borate, magnesiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, calciumtetrakispentafluorophenyl)borate, calcium(octyloxy)tris(pentafluorophenyl)borate, calciumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, lithium tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,sodiumtetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,silvertetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,thalliumtetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,lithiumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,sodiumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,silvertetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,thalliumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,lithiumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,sodiumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,silvertetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,thalliumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,trimethylsilylium tetrakis(pentafluorophenyl)borate, trimethylsilyliumetherate tetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, triphenylsilyliumtetrakis(pentafluorophenyl)borate, tris(mesityl)silyliumtetrakis(pentafluorophenyl)borate, tribenzylsilyliumtetrakis(pentafluorophenyl)borate, trimethylsilyliummethyltris(pentafluorophenyl)borate, triethylsilyliummethyltris(pentafluorophenyl)borate, triphenylsilyliummethyltris(pentafluorophenyl)borate, tribenzylsilylium methyltris(pentafluorophenyl)borate, trimethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, tribenzylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, trimethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, trimethylsilyliumtetrakis(3,4,5-trifluorophenyl)borate, tribenzylsilyliumtetrakis(3,4,5-trifluorophenyl)aluminate, triphenylsilyliummethyltris(3,4,5-trifluorophenyl)aluminate, triethylsilyliumtetrakis(1,2,2-trifluoroethenyl)borate, tricyclohexylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, dimethyloctadecylsilyliumtetrakis(pentafluorophenyl)borate, tris(trimethyl)silyl)silyliummethyltri(2,3,4,5-tetrafluorophenyl)borate,2,2′-dimethyl-1,1′-binaphthylmethylsilyliumtetrakis(pentafluorophenyl)borate,2,2′-dimethyl-1,1′-binaphthylmethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, lithiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate, trityl(perfluorobiphenyl)fluoroaluminate,lithium(octyloxy)tris(pentafluorophenyl)aluminate, lithiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, sodiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate,sodium(octyloxy)tris(pentafluorophenyl)aluminate, sodiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, potassiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate, potassium(octyloxy)tris(pentafluorophenyl)aluminate, potassiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, magnesiumtetrakis(pentafluorophenyl)aluminate,magnesium(octyloxy)tris(pentafluorophenyl)aluminate, magnesiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, calciumtetrakis(pentafluorophenyl)aluminate, calcium(octyloxy)tris(pentafluorophenyl)aluminate, and calciumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate.

Examples of WCA salts having a weakly coordinating anion described underFormula III include but are not limited to LiB(OC(CF₃)₃)₄,LiB(OC(CF₃)₂(CH₃))₄, LiB(OC(CF₃)₂H)₄, LiB(OC(CF₃)(CH₃)H)₄,TlB(OC(CF₃)₃)₄, TlB(OC(CF₃)₂H)₄, TlB(OC(CF₃)(CH₃)H)₄,TlB(OC(CF₃)₂(CH₃))₄, (Ph₃C)B(OC(CF₃)₃)₄, (Ph₃C)B(OC(CF₃)₂(CH₃))₄,(Ph₃C)B(OC(CF₃)₂H)₄, (Ph₃C)B(OC(CF₃)(CH₃)H)₄, AgB(OC(CF₃)₃)₄,AgB(OC(CF₃)₂H)₄, AgB(OC(CF₃)(CH₃)H)₄, LiB(O₂C₆F₄)₂, TlB(O₂C₆F₄)₂,Ag(toluene)₂B(O₂C₆F₄)₂, and Ph₃CB(O₂C₆F₄)₂, LiB(OCH₂(CF₃)₂)₄,[Li(HOCH₃)₄]B(O₂C₆Cl₄)₂, [Li(HOCH₃)₄]B(O₂C₆F₄)₂,[Ag(toluene)₂]B(O₂C₆Cl₄)₂, LiB(O₂C₆Cl₄)₂, (LiAl(OC(CF₃)₂Ph)₄),(TlAl(OC(CF₃)₂Ph)₄), (AgAl(OC(CF₃)₂Ph)₄), (Ph₃CAl(OC(CF₃)₂Ph)₄,(LiAl(OC(CF₃)₂C₆H₄CH₃)₄), (ThAl(OC(CF₃)₂C₆H₄CH₃)₄),(AgAl(OC(CF₃)₂C₆H₄CH₃)₄), (Ph₃CAl(OC(CF₃)₂C₆H₄CH₃)₄), LiAl(OC(CF₃)₃)₄,ThAl(OC(CF₃)₃)₄, AgAl(OC(CF₃)₃)₄, Ph₃CAl(OC(CF₃)₃)₄,LiAl(OC(CF₃)(CH₃)H)₄, TlAl(OC(CF₃)(CH₃)H)₄, AgAl(OC(CF₃)(CH₃)H)₄,Ph₃CAl(OC(CF₃)(CH₃)H)₄, LiAl(OC(CF₃)₂H)₄, TlAl(OC(CF₃)₂H)₄,AgAl(OC(CF₃)₂H)₄, Ph₃CAl(OC(CF₃)₂H)₄, LiAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄,TlAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄, AgAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄, LiAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄,TlAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄, AgAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄, LiAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄,TlAl(OC(CF₃)₂C₆H₄-4-Si Me₃)₄, AgAl(OC(CF₃)₂C₆H₄-4-Si Me₃)₄,Ph₃CAl(OC(CF₃)₂C₆H4-4-Si Me₃)₄, LiAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,TlAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄, AgAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,LiAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,TlAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,AgAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,Ph₃CAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,LiAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄, TlAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄,AgAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄, Ph₃CAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄,LiAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄, TlAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄,AgAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄, Ph₃CAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄,LiAl(OC(CF₃)₂C₆F₅)₄, TlAl(OC(CF₃)₂C₆F₅)₄, AgAl(OC(CF₃)₂C₆F₅)₄, andPh₃CAl(OC(CF₃)₂C₆F₅)₄.

Examples of boratobenzene salts include but are not limited to[1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-borinyl lithium,[1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-borinyltriphenylmethylium,4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borinyl lithium,4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borinyltriphenylmethylium, 1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borinyllithium, 1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borinyltriphenylmethylium,1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borinyllithium, and1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borinyltriphenylmethylium.

Examples of WCA carborane and halocarborane salts include but are notlimited to silver dodecahydro-1-carbadodecaborate, LiCB₁₁(CH₃)₁₂,LiCB₁₁H₁₂, (Me₃NH)[CB₁₁H₁₂], (Me₄N)[1-C₂H₅CB₁₁H₁₁],(Me₄N)[1-Ph₃SiCB₁₁H₁₁], (Me₄N)[1-CF₃CB₁₁H₁₁], Cs[12-BrCB₁₁H₁₁],Ag[12-BrCB₁₁H₁₁], Cs[7,12-Br₂CB₁₁H₁₀], Cs[12-ClCB₁₁H₁₁],Cs[7,12-Cl₂CB₁₁H₁₀], Cs[1-H-CB₁₁F₁₁], Cs[1-CH₃-CB₁₁F₁₁],(i-Pr₃)Si[1-CF₃-CB₁₁F₁₁], Li[12-CB₁₁H₁₁F], Li[7,12-CB₁₁H₁₁F₂],Li[7,9,12-CB₁₁H₁₁F₃], (i-Pr₃)Si[CB₁₁H₆Br₆], Cs[CB₁₁H₆Br₆], Li[6-CB₉H₉F],Li[6,8-CB₉H₈F₂], Li[6,7,8-CB₉H₇F₃], Li[6,7,8,9-CB₉H₆F₄],Li[2,6,7,8,9-CB₉H₅F₅], Li[CB₉H₅Br₅], Ag[CB₁₁H₆Cl₆], Tl[CB₁₁H₆Cl₆],Ag[CB₁₁H₆F₆], Tl[CB₁₁H₆F₆], Ag[CB₁₁H₆I₆], Tl[CB₁₁H₆I₆], Ag[CB₁₁H₆Br₆],Tl[CB₁₁H₆Br₆], Li[6,7,9,10,11,12-CB₁₁H₆F₆], Li[2,6,7,8,9,10-CB₉H₅F₅],Li[1-H-CB₉F₉], Tl[12-CB₁₁H₁₁(C₆H₅)], Ag[1-C₆F₅-CB₁₁H₅Br₆], Li[CB₁₁Me₁₂],Li[CB₁₁(CF₃)₁₂], Li[CB₁₁H₆I₆], Li[CB₉H₅Br₅], Li[Co(B₉C₂H₁₁)₂],Li[CB₁₁(CH₃)₁₂], Li[CB₁₁(C₄H₉)₁₂], Li[CB₁₁(C₆H₁₃)₁₂], Na[Co(C₂B₉H₁₁)₂],and Na[Co(Br₃C₂B₉H₈)₂]. Additional halocarborane salts are disclosed inInternational Patent Publication WO 98/43983.

Monomers

The catalysts of the present invention are suitable for the preparationof a wide range of polymers comprising cyclic repeating units. Thecyclic polymers are prepared by the addition polymerization of apolycycloolefin monomer(s) in the presence of a catalytic amount of acatalyst of Formula I or the procatalyst components described above. Themonomer(s) can be polymerized via solution or mass polymerizationtechniques. As stated herein the terms “polycycloolefin,” “polycyclic,”and “norbornene-type” monomer are used interchangeably and mean that themonomer contains at least one norbornene moiety as shown below:

The simplest polycyclic monomer of the invention is the bicyclicmonomer, bicyclo[2.2.1]hept-2-ene, commonly referred to as norbornene.The term norbornene-type monomer is meant to include norbornene,substituted norbornene(s), and any substituted and unsubstituted highercyclic derivatives thereof so long as the monomer contains at least onenorbornene-type or substituted norbornene-type moiety. Preferredsubstituted norbornene-type monomers and higher cyclic derivativesthereof contain a pendant hydrocarbyl substituent(s) or a pendantfunctional substituent(s) containing an oxygen atom. The preferrednorbornene-type or polycycloolefin monomers are represented by thestructure below:

wherein “a” represents a single or double bond, R¹ to R⁴ independentlyrepresents a hydrocarbyl or functional substituent, m is an integer from0 to 5, and when “a” is a double bond one of R¹, R² and one of R³, R⁴ isnot present.

When the substituent is a hydrocarbyl group, halohydrocarbyl, orperhalocarbyl group R¹ to R⁴ independently represent hydrocarbyl,halogenated hydrocarbyl and perhalogenated hydrocarbyl groups selectedfrom hydrogen, linear and branched C₁-C₁₀ alkyl, linear and branched,C₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ alkynyl, C₄-C₁₂ cycloalkyl,C₄-C₁₂ cycloalkenyl, C₆-C₁₂ aryl, and C₇-C₂₄ aralkyl, R¹ and R² or R³and R⁴ can be taken together to represent a C₁-C₁₀ alkylidenyl group.Representative alkyl groups include but are not limited to methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl.Representative alkenyl groups include but are not limited to vinyl,allyl, butenyl, and cyclohexenyl. Representative alkynyl groups includebut are not limited to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and2-butynyl. Representative cycloalkyl groups include but are not limitedto cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representativearyl groups include but are not limited to phenyl, naphthyl, andanthracenyl. Representative aralkyl groups include but are not limitedto benzyl, and phenethyl. Representative alkylidenyl groups includemethylidenyl, and ethylidenyl, groups.

The preferred perhalohydrocarbyl groups include perhalogenated phenyland alkyl groups. The halogenated alkyl groups useful in the inventionare linear or branched and have the formula C_(z)X″_(2z+1) wherein X″ isa halogen as set forth above and z is selected from an integer of 1 to10. Preferably X″ is fluorine. Preferred perfluorinated substituentsinclude perfluorophenyl, perfluoromethyl, perfluoroethyl,perfluoropropyl, perfluorobutyl, and perfluorohexyl. In addition to thehalogen substituents, the cycloalkyl, aryl, and aralkyl groups of theinvention can be further substituted with linear and branched C₁-C₅alkyl and haloalkyl groups, aryl groups and cycloalkyl groups.

When the pendant group(s) is a functional substituent, R¹ to R⁴independently represent a radical selected from —(CH₂)_(n)C(O)NH₂,—(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵, —(CH₂)_(n)—OC(O)R⁵,—(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵, —(CH₂)_(n)SiR⁵,—(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)C(O)OR⁶, and the group:

wherein n independently represents an integer from 0 to 10 and R⁵independently represents hydrogen, linear and branched C₁-C₁₀ alkyl,linear and branched, C₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ alkynyl,C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, and C₇-C₂₄ aralkyl. Representativehydrocarbyl groups set forth under the definition of R⁵ are the same asthose identified above under the definition of R¹ to R⁴. As set forthabove under R¹ to R⁴ the hydrocarbyl groups defined under R⁵ can behalogenated and perhalogenated. The R⁶ radical represents an acid labilemoiety selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃,—CH(R⁷)OC(CH₃)₃ or the following cyclic groups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup. The alkyl groups include methyl, ethyl, propyl, i-propyl, butyl,i-butyl, t-butyl, pentyl, t-pentyl and neopentyl. In the abovestructures, the single bond line projecting from the cyclic groupsindicates the position where the cyclic protecting group is bonded tothe acid substituent. Examples of R⁶ radicals include1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl,2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl,3-oxocyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl, and 1-t-butoxyethyl.

The R⁶ radical can also represent dicyclopropylmethyl (Dcpm), anddimethylcyclopropylmethyl (Dmcp) groups which are represented by thefollowing structures:

In Structure VII above, R¹ and R⁴ together with the two ring carbonatoms to which they are attached can represent a substituted orunsubstituted cycloaliphatic group containing 4 to 30 ring carbon atomsor a substituted or unsubstituted aryl group containing 6 to 18 ringcarbon atoms or combinations thereof. The cycloaliphatic group can bemonocyclic or polycyclic. When unsaturated the cyclic group can containmonounsaturation or multiunsaturation, with monounsaturated cyclicgroups being preferred. When substituted, the rings containmonosubstitution or multisubstitution wherein the substituents areindependently selected from hydrogen, linear and branched C₁-C₅ alkyl,linear and branched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy,halogen, or combinations thereof. R¹ and R⁴ can be taken together toform the divalent bridging group, —C(O)—Q—(O)C—, which when takentogether with the two ring carbon atoms to which they are attached forma pentacyclic ring, wherein Q represents an oxygen atom or the groupN(R⁸), and R⁸ is selected from hydrogen, halogen, linear and branchedC₁-C₁₀ alkyl, and C₆-C₁₈ aryl. A representative structure is shown inbelow.

wherein m is an integer from 0 to 5.

Deuterium enriched norbornene-type monomers wherein at least one of thehydrogen atoms on the norbornene-type moiety and/or one at least one ofthe hydrogen atoms on a pendant hydrocarbyl substituent described underR¹ to R⁴ have been replaced by a deuterium atom are contemplated withinthe scope of the present invention. Preferably at least 40 percent ofthe hydrogen atoms on the norbornene-type moiety and/or the hydrocarbylsubstituent are replaced by deuterium, more preferably, at least about50 percent, and still more preferably at least about 60 percent.Preferred deuterated monomers are represented by the structure below:

wherein R^(D) is deuterium, “i” is an integer ranging from 0 to 6, withthe proviso that when “i” is 0, at least one of R^(1D) and R^(2D) mustbe present, R¹ and R² independently represent a hydrocarbyl orfunctional substituent as defined above, and R^(1D) and R^(2D) may ormay not be present and independently represent a deuterium atom or adeuterium enriched hydrocarbyl group containing at least one deuteriumatom. Preferably the deuterated hydrocarbyl group is selected fromlinear and branched C₁-C₁₀ alkyl wherein at least 40 percent, preferablyat least 50 percent and more preferably at least 60 percent of thehydrogen atoms on the carbon backbone are replaced by deuterium.

Crosslinked polymers can be prepared by copolymerizing thenorbornene-type monomer(s) set forth under Structure VII above with amultifunctional norbornene-type or multifunctional polycycloolefincrosslinking monomer(s). By multifunctional norbornene-type ormultifunctional polycycloolefin crosslinking monomer is meant that thecrosslinking monomer contains at least two norbornene-type moieties,each functionality being addition polymerizable in the presence of thecatalyst system of the present invention. The crosslinkable monomersinclude fused multicyclic ring systems and linked multicyclic ringsystems. Examples of fused crosslinkers are illustrated in StructuresVIIb to VIIg below. For brevity, norbornadiene is included as a fusedmulticyclic crosslinker.

wherein m independently is an integer from 0 to 5.

A linked multicyclic crosslinker is illustrated generically in StructureVIII below.

wherein m independently is an integer from 0 to 5, R⁹ is a divalentradical selected from divalent hydrocarbyl radicals and divalent etherradicals. By divalent is meant that a free valence at each terminal endof the radical is attached to a norbornene-type moiety. Preferreddivalent hydrocarbyl radicals are alkylene radicals and divalentaromatic radicals. The alkylene radicals are represented by the formula—(C_(d)H_(2d))— where d represents the number of carbon atoms in thealkylene chain and is an integer from 1 to 10. The alkylene radicals arepreferably selected from linear and branched (C₁-C₁₀) alkylene such asmethylene, ethylene, propylene, butylene, pentylene, hexylene,heptylene, octylene, nonylene, and decylene. When branched alkyleneradicals are contemplated, it is to be understood that a hydrogen atomin the alkylene backbone is replaced with a linear or branched (C₁ toC₅) alkyl group.

The divalent aromatic radicals are selected from divalent phenyl, anddivalent naphthyl radicals. The divalent ether radicals are representedby the group —R¹⁰—O—R¹⁰—, wherein R¹⁰ independently is the same as R⁹.Examples of specific linked multicyclic crosslinkers are represented asin Structures VIIIa to VIIIe as follows.

An economical route for the preparation of hydrocarbyl substituted andfunctionally substituted norbornene monomers relies on the Diels-Alderaddition reaction in which CPD or substituted CPD is reacted with asuitable dienophile at elevated temperatures to form the substitutednorbornene-type adduct generally shown by the following reaction scheme:

wherein R¹ to R⁴ independently represent hydrogen, hydrocarbyl, and/or afunctional group as previously described.

Other norbornene type adducts can be prepared by the thermal pyrolysisof dicyclopentadiene (DCPD) in the presence of a suitable dienophile.The reaction proceeds by the initial pyrolysis of DCPD to CPD followedby the Diels-Alder addition of CPD and the dienophile to give theadducts shown below:

wherein n represents the number of cyclic units in the monomer and R¹ toR⁴ independently represent hydrogen, hydrocarbyl, and/or a functionalgroup as previously defined. Norbornadiene and higher Diels-Alderadducts thereof similarly can be prepared by the thermal reaction of CPDand DCPD in the presence of an acetylenic reactant as shown below.

wherein n, R¹ and R² are as defined above.

Deuterium enriched norbornene-type monomers can be prepared by heatingDCPD in the presence of D₂O and a base such as NaOH to yield deuteratedCPD which in turn can be reacted with a dienophile (Eq. 1) or adeuterated dienophile (Eq. 2) to give the respective deuteratednorbornene containing a pendant deuterated hydrocarbyl substituent or apendant hydrocarbyl substituent. In another embodiment non-deuteratedCPD can be reacted with a deuterium enriched dienophile to yieldnorbornene containing a deuterium enriched hydrocarbyl pendant group(Eq. 3).

In Eq. 1 and Eq. 2 above, R¹ to R⁴, R^(1D) and R^(2D) are as previouslydefined, and i′ is an integer ranging from 1 to 6.

Examples of polymerizable norbornene-type monomers include but are notlimited to norbornene (bicyclo[2.2.1]hept-2-ene),5-ethylidenenorbornene, dicyclopentadiene,tricyclo[5.2.1.0^(2.6)]deca-8-ene,5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylic acid,5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene,5-ethoxycarbonylbicyclo[2.2.1]hept-2-ene,5-n-propoxycarbonylbicyclo[2.2.1]hept-2-ene,5-i-propoxycarbonylbicyclo[2.2.1]hept-2-ene,5-n-butoxycarbonylbicyclo[2.2.1]hept-2-ene,5-(2-methylpropoxy)carbonylbicyclo[2.2.1]hept-2-ene,5-(1-methylpropoxy)carbonylbicyclo[2.2.1]hept-2-ene,5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene,5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-(4′-t-butylcyclohexyloxy)carbonylbicyclo[2.2.1]hept-2-ene,5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene,5-tetrahydrofuranyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-tetrahydropyranyloxycarbonylbicyclo[2.2.1]hept-2-ene,bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, 5-acetyloxybicyclo[2.2.1]hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-ethoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-n-propoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-i-propoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-n-butoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-(2-methylpropoxy)carbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-(1-methylpropoxy)carbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-(4′-t-butylcyclohexyloxy)carbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-tetahydrofuranyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-tetrahydropyranyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-acetyloxybicyclo[2.2.1]hept-2-ene,5-methyl-5-cyanobicyclo[2.2.1]hept-2-ene,5,6-di(methoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(ethoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(n-propoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(i-propoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(n-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(henoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(tetrahydrofuranyloxycarbonyl)bicyco[2.2.1]hept-2-ene,5,6-di(tetrahydropyranyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, and5,6-dicarboxyanhydridebicyclo[2.2.1]hept-2-ene,8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-ethoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-n-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene ,8-i-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-n-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-(2-methylpropoxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-(1-methylpropoxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-t-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-cyclohexyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-(4′-t-butylcyclohexyloxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-phenoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-tetrahydrofuranyloxycarbonyltetracyclo[4.4.0.1^(2,5)1^(7,10)]-3-dodecene,8-tetrahydropyranyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-acetyloxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-i-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-(2-methylpropoxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-(1-methylpropoxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-t-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-cyclohexyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-(4′-t-butylcyclohexyloxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-phenoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-tetrahydrofuranyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene,8-methyl-8-tetrahydropyranyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene,8-methyl-8-acetyloxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-cyanotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(methoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(ethoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(n-propoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(i-propoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(n-butoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(t-butoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(cyclohexyloxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(phenoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(tetrahydrofuranyloxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene,8,9-di(tetrahydropyranyloxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene,8,9-dicarboxyanhydridetetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene-8-carboxylic acid,8-methyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene-8-carboxylic acid,8-methyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-ethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-fluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-fluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-difluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-trifluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-pentafluoroethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8-difluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-difluorotetracyclo[4.4. 0.1^(2,5).1^(7,10)]dodec-3-ene,8,8-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-trifluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-trifluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-tris(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9,9-tetrafluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9,9-tetrakis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8-difluoro-9,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5.)1^(7,10)]dodec-3-ene,8,9-difluoro-8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-trifluoro-9-trifluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-trifluoro-9-trifluoromethoxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-trifluoro-9-pentafluoropropoxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-fluoro-8-pentafluoroethyl-9,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-chloro-8,9,9-trifluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-dichloro-8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-(2,2,2-trifluorocarboxyethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-(2,2,2-trifluorocarboxyethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,tricyclo[4.4.0.1^(2,5)]undeca-3-ene,tricyclo[6.2.1.0^(1,8)]undeca-9-ene,tetracyclo[4.4.0.1^(2,5).1^(7,10.0)]dodec-3-ene,8-methyltetracyclo[4.4.0.1²⁵.1^(7,10).0^(1,6)]dodec-3-ene,8-ethylidenetetracyclo[4.4.0.1^(2,5).1^(7,12)]dodec-3-ene,8-ethylidenetetracyclo[4.4.0.1^(2,5).1^(7,10).0^(1,6)]dodec-3-ene,pentacyclo[6.5.1.1^(3,6).0^(2,7).0^(9,13)]pentadeca-4-ene, andpentacyclo[7.4.0.1^(2,5).1^(9,12).0^(8,13)]pentadeca-3-ene

In another embodiment of the invention the polymer can be crosslinkedduring a post polymerization curing step (latent crosslinking). In thisembodiment a norbornene-type monomer containing a pendant postcrosslinkable functional group is copolymerized into the polycyclicbackbone whereupon the functional group is subsequently crosslinked viawell known techniques. By post crosslinkable functional group is meantthat the functional group is inert to the initial polymerizationreaction but is receptive to subsequent chemical reactions to effect thecrosslinking of adjacent polymer chains. Suitable post crosslinkablemonomers are set forth under Structure VII wherein at least one of R¹ toR⁴ is selected from linear and branched, C₂-C₁₀ alkenyl, C₄-C₁₀cycloalkenyl, —(CH₂)_(n)Si(OR⁵)₃, wherein n and R⁵ are as defined above,R¹ and R² or R³ and R⁴ can be taken together to represent a C₁-C₁₀alkylidenyl radical, fused cyclic groups wherein R¹ and R⁴ takentogether with the two ring carbon atoms to which they are attached forman unsaturated C₄ to C₈ ring. Preferred post crosslinkable alkenylfunctional groups include vinyl, butenyl, and cyclohexyl. Preferredalkylidenyl groups include methylidenyl and ethylidenyl substituents.Preferred alkoxysilyl groups include trimethoxysilyl and triethoxysilylmoieties. Preferred crosslinkers containing fused multicyclic ringsystems include dicyclopentadiene (DCPD) and unsymmetrical trimer ofcyclopentadiene (CPD).

The latent crosslinkable pendant groups can be reacted via a varietychemistries known to initiate the reaction of the various functionalgroups. For example, the alkenyl, cycloalkenyl, and alkylidenyl groupscan be crosslinked via a free radical mechanism. The alkoxysilyl groupscan be crosslinked via a cationic reaction mechanism. Representativemonomers that contain post crosslinkable functional groups arerepresented below.

In the latent crosslinking embodiment of the invention the crosslinkingreaction step can be induced by a free radical initiator. Suitableinitiators are those that can be activated thermally or photochemically.The initiator is added to the reaction medium and the polymerization ofthe monomer mixture is allowed to proceed to completion. A keyconsideration, however, is that the radical generating compound employedbe stable (does not decompose) at the polymerization temperature of themonomeric reaction medium. When utilizing thermally activated freeradical generators, latent crosslinking is induced by exposing thepolymer medium to temperatures above the decomposition temperature ofthe free radical generating compound. In embodiments utilizingphotoinitiated free radical generators, latent crosslinking is inducedby exposing the polymer medium to a radiation source such as e-beam andUV radiation. Suitable free radical generator compounds (crosslinkingagents) include the organic peroxides and aliphatic azo compounds. Thealiphatic azo compounds are suitable initiators for the thermal andphotochemical activated crosslinking embodiments of the invention, whilethe organic peroxides are suitable for use in as thermally activatedinitiators only. The amount of crosslinking agent employed ranges fromabout 0.005 part by weight to about 5.0 parts by weight based on 100parts by weight of monomer in the reaction medium.

Suitable organic peroxide include but are not limited to dibenzoylperoxide, di(2,4-dichlorobenzoyl) peroxide, diacetyl peroxide,diisobutyryl peroxide, dilauroyl peroxide, t-butylperbenzoate,t-butylperacetate, 2,5-di(benzoylperoxy)-1,2-dimethylhexane, di-t-butyldiperoxyazelate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroctoate,2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane,t-butylperoxyneodecanoate, ethyl 3,3-di(t-butylperoxy)butyrate,2,2-di(t-butylperoxy)butane, 1,1-di(t-butylperoxy)cyclohexane,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,2,5-di(t-butylperoxy)-2,5-dimethylhex-3-yne, di-t-butyl peroxide,2,5-di(t-butylperoxy)-2,5-dimethylhexane, dicumyl peroxide, n-propylperoxydicarbonate, i-propyl peroxydicarbonate, cyclohexylperoxydicarbonate, and acetyl peroxydicarbonate.

Suitable azo compounds include but are not limited to2,2′-azobis[2,4-dimethyl]pentane,2-(t-butylazo)-4-methoxy-2,4-dimethylpentanenitrile,2,2′-azobis(i-butyronitrile), 2-(t-butylazo)-2,4-dimethylpentanenitrile,2-(t-butylazo)i-butyronitrile, 2-(t-butylazo)-2-methylbutanenitrile,1,1-azobis-cyclohexanecarbonitrile,1-(t-amylazo)cyclohexanecarbonitrile, and1-(t-butylazo)cyclohexanecarbonitrile.

The decomposition temperatures of the foregoing free radical generatorcompounds are well known in the art and can be selected on the basis ofthe polymerization temperatures employed in initial reaction. In otherwords the initiator compound must be stable at the polymerizationtemperatures so it is available for the post polymerization crosslinkingreaction. As discussed above latent crosslinking is can be effected bythermal or photochemical means.

As discussed above, monomers containing trialkoxysilyl groups can becrosslinked by latent crosslinking in the presence of a cationicinitiator agent. A polymerization stable cationic initiator can be canbe thermally activated to induce the latent crosslinking of the silylgroups. Suitable cationic crosslinking initiators include, for example,dibutyltin diluarate, dimethyltin diluarate, and dioctyltin diluarate.

The amount of multifuinctional norbornene-type crosslinkable monomersand post crosslinkable monomers that are optionally present in thereaction mixture can range from about 0.1mole percent to about 50 molepercent based on the total monomer in the monomer mixture to be reacted.Preferably, the amount of crosslinker ranges from about 1mole percent toabout 25 mole percent of the total monomer mixture and most preferablyfrom about 1mole percent to about 10 mole percent.

Monomer Polymerization

The monomers of the invention are polymerized in solution or in mass.The catalyst is added to the reaction medium containing the desiredmonomer(s) as a preformed single component catalyst or the catalyst canbe formed in situ by admixing the procatalyst component, the Group 15electron donor component, and the WCA salt activator component in thereaction medium. When the procatalyst is ligated with the Group 15electron donor component, it is not necessary to employ the Group 15electron donor as a separate component. In one in situ embodiment theligated procatalyst component (e.g., containing desired ligand group(s))is admixed with the WCA salt activator component in the reaction medium.In another in situ embodiment a procatalyst component with or withoutligands is admixed with a desired ligand containing component(s) and theWCA salt activator component in the reaction medium. The procatalystcomponents are generically exemplified in the preformed catalystpreparation equations (1) to (4) set forth above. The preferred molarratio of procatalyst (based on the Group 10 metal): Group 15 electrondonor component: WCA salt is 1:1-10:1-100, more preferably, 1:1-5:1-20,and most preferably, 1:1-2:1-5. In embodiments of the invention wherethe procatalyst is ligated with a Group 15 electron donor ligand and/ora labile neutral electron donor ligand, the molar ratio of procatalyst(based on the metal content) to WCA salt 1:1-100, preferably, 1:1-20,and more preferably, 1:1-5. The order of addition of the variouscatalyst components to the reaction medium is not important.

The polymers prepared by the process of the invention are additionpolymers of polycycloolefinic repeating units linked through2,3-enchainment. The repeating units are polymerized from apolycycloolefin monomer or combination of polycycloolefin monomers thatcontain at least one norbornene-type moiety as described herein.

Solution Process

In the solution process the polymerization reaction can be carried outby adding a solution of the preformed catalyst or individual catalystcomponents to a solution of the cycloolefin monomer or mixtures ofmonomers to be polymerized. The amount of monomer in solvent preferablyranges from 10 to 50 weight percent, and more preferably 20 to 30 weightpercent. After the single component catalyst or catalyst components areadded to the monomer solution, the reaction medium is agitated (e.g.,stirred) to ensure complete mixing of catalyst and monomer components.

The polymerization reaction temperatures can range from about 0° C. toabout 150° C., preferably from about 10° C. to about 100° C., and morepreferably from about 20° C. to about 80° C.

Examples of solvents for the polymerization reaction include but are notlimited to alkane and cycloakane solvents such as pentane, hexane,heptane, and cyclohexane; halogenated alkane solvents such asdichloromethane, chloroform, carbon tetrachloride, ethylchloride,1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane,2-chloropropane, 1-chlorobutane, 2-chlorobutane,1-chloro-2-methylpropane, and 1-chloropentane; aromatic solvents such asbenzene, xylene, toluene, mesitylene, chlorobenzene, ando-dichlorobenzene, Freon® 112 halocarbon solvent, water; or mixturesthereof. Preferred solvents include cyclohexane, toluene, mesitylene,dichloromethane, 1,2-dichloroethane, and water.

Surprisingly, it has been found that the catalysts of the invention arehighly active in the polymerization of cycloolefins. The catalystsexhibit activities at monomer to procatalyst or catalyst metal molarratios of over 100,000:1. Preferred monomer to procatalyst or catalystratios range from about 100,500:1to about 1,000,000:1, more preferablyfrom about 110,000:1to about 500,000:1and most preferably from about120,000:1to about 250,000:1. While these catalysts have been found to beactive at monomer to catalyst metal molar ratios of over 100,000:1, itis within the scope of this invention to utilize monomer to catalystmetal molar ratios of less than 100,000:1depending on the use desiredfor the polymer.

When an aqueous polymerization medium is desired it is preferable thatthe Group 15 electron donor ligand or component be chosen from the watersoluble phosphines set forth above. The polymerization reaction can beconducted in suspension or emulsion. In suspension, the monomers aresuspended in an aqueous medium containing a suspension agent selectedfrom one or more water soluble substances such as, for example,polyvinyl alcohol, cellulose ether, partially hydrolyzed polyvinylacetate, or gelatin and then carrying out the reaction in the presenceof the catalyst system of the invention.

The emulsion polymerization can in general be carried out by emulsifyingthe monomers in water or a mixed solvent of water and a water-miscibleorganic solvent (such as methanol, or ethanol), preferably in thepresence of at least one emulsifying agent and then carrying out theemulsion polymerization in the presence of the catalyst of theinvention. Emulsifying agents include, for example, mixed acid soapscontaining fatty and rosin acids, alkyl sulfonate soaps and soaps ofoligomeric naphthalene sulfonates.

Mass Process

In the mass polymerization process according to the invention a twocomponent catalyst system is preferably employed in the polymerizationof the cycloolefinic monomer(s). The term mass polymerization refers toa polymerization reaction which is generally carried out in thesubstantial absence of a solvent. In some cases, however, a smallproportion of solvent is present in the reaction medium. Small amountsof solvent can be conveyed to the reaction medium via the introductionof the catalyst system components which are in some cases dissolved insolvent. Solvents also can be employed in the reaction medium to reducethe viscosity of the polymer at the termination of the polymerizationreaction to facilitate the subsequent use and processing of the polymer.The amount of solvent that can be present in the reaction medium rangesfrom 0 to about 20 percent, preferably from 0 to about 10 percent and,more preferably from 0 to about 1percent, based on the weight of themonomer(s) present in the reaction mixture. Preferred solvents are thosethat are utilized in dissolving the catalyst system components. Examplesof solvents include but are not limited to alkane and cycloalkanesolvents such as pentane, hexane, heptane, and cyclohexane; halogenatedalkane solvents such as dichloromethane, chloroform, carbontetrachloride, ethylchloride, 1,1-dichloroethane, 1,2-dichloroethane,1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane,1-chloro-2-methylpropane, and 1-chloropentane; esters such asethylacetate, i-amylacetate; ethers such as THF and diethylether;aromatic solvents such as benzene, xylene, toluene, mesitylene,chlorobenzene, and o-dichlorobenzene; and halocarbon solvents such asFreon® 112; and mixtures thereof. Preferred solvents include benzene,fluorobenzene, o-difluorobenzene, p-difluorobenzene, pentafluorobenzene,hexafluorobenzene, o-dichlorobenzene, chlorobenzene, toluene, o-, m-,and p-xylenes, mesitylene, cyclohexane, ethylacetate, THF, anddichloromethane.

A ligated procatalyst containing a Group 15 electron donor ligand isprepared in solvent and then added to the desired monomer or mixture ofmonomers containing the dissolved WCA salt activator. The reactionmixture is mixed and the reaction is permitted to proceed from about1minute to about 2 hours. The reaction mixture can be optionally heatedat a temperature ranging from about 20° C. to about 200° C. Thepolymerization temperature is not specifically limited, but is usuallyin the range of 20° C. to 120° C., preferably 20° C. to 90° C. Thepolymerization reaction can be carried out under an inert atmospheresuch as nitrogen or argon. Advantageously, however, it has been foundthat the catalyst system components of the invention are moisture andoxygen insensitive, allowing for less stringent handling and processingconditions. Following the initial polymerization reaction a polymercement is obtained. The cement can be applied to a desired substrate orconveyed into a mold and post cured to complete the polymerizationreaction.

Without wishing to be bound by theory of invention it is believed thatpost curing is desirable from the standpoint of monomer to polymerconversion. In a mass process the monomer is essentially the diluent forthe catalyst system components. As monomer is converted to polymer aplateau is reached beyond which conversion of monomer to polymer can gono higher (vitrification). This conversion barrier results from the lossof reactant mobility as the reaction medium becomes converted to apolymeric matrix. Consequently, the catalyst system components andunconverted monomer become segregated and can not react. It is wellknown that diffusivity within a polymer decreases dramatically as thepolymer passes from the rubbery state to the glassy state. It isbelieved that post curing at elevated temperatures increases themobility of the reactants in the matrix allowing for the furtherconversion of monomer to polymer.

Post curing of the polymers of the present invention is preferablyconducted at elevated temperatures for a time period sufficient to reacha desired conversion of monomer to polymer. The post curing cycle ispreferably conducted for 1to 2 hours over a temperature range of fromabout 100° C. to about 300° C., preferably from about 125° C. to about200 ° C., and more preferably from about 140° C. to about 180 ° C. Thecure cycle can be effected at a constant temperature or the temperaturecan be ramped, e.g., incrementally increasing the curing temperaturefrom a desired minimum curing temperature to a desired maximum curingtemperature over the desired curing cycle time range. In one embodiment(A) the temperature ramping can be effected by following a gradualincreasing slope on a temperature vs. time plot from the desired minimumtemperature to the desired maximum temperature in the cure cycle. Inthis embodiment when the maximum temperature is reached, the temperaturemaximum can optionally be held for a desired period of time until thedesired cure state is attained. In an alternate embodiment (B) thetemperature ramping can follow a stepwise curve on a temperature vs.time plot. In this embodiment the temperature ramping proceeds in stepfashion from the desired minimum cure temperature to the desired maximumcure temperature in the cure cycle. In another embodiment (C) the postcure can be effected by combining post cure embodiments (A and B)whereinthe cure cycle encompasses a combination of steps and slopes from thedesired minimum cure temperature to the desired maximum curetemperature. In still another embodiment (D and E) the cure cycle canfollow a curve from the desired minimum cure temperature to the desiredmaximum cure temperature. In embodiments A, B, and C it should be notedthat the rise and run of the slope do not have to be constant betweenthe minimum and maximum cure temperatures of the cure cycle. In otherwords the rise and run can vary when proceeding from the desired minimumto desired maximum cure temperatures The foregoing cure cycletemperature ramping curves are illustrated below.

Ramping of the temperature during the cure cycle is preferable becauseit diminishes the potential for catalyst degradation and the boiling ofunconverted monomer.

Optionally, additives include but not limited to those selected from ofblowing agents, foaming agents, pigments, dyes, fillers such as mica,germania, titania, zirconia, boron nitrides, silicon nitrides, siliconcarbides, barium titanate, lead magnesium niobate-lead titanate(Tamtron® Y5V183U dielectric filler available from Tam Ceramics), goldcoated polymer latices, silver particles, plasticizers, lubricants,flame retardants, tackifiers, antioxidants, fibers, antioxidants, UVstabilizers, masking agents, odor absorbing agents, crosslinking agents,tougheners and impact modifiers, polymeric modifiers and viscosifiersand mixtures thereof, can be added by mixing one or more of them intothe monomer medium before the polymerization reaction is initiated. Theidentity and relative amounts of such components are well known to thoseskilled in the art and need not be discussed in detail here.

The optional additives are employed to enhance the processing,appearance and/or the physical properties of the polymer. For example,the additives can be utilized to enhance and modify inter alia thecoefficient of thermal expansion, stiffness, impact strength, dielectricconstant, solvent resistance, color, and odor of the polymer product.The viscosifiers are employed to modify the viscosity and shrinkage ofthe monomeric mixture before the polymerization reaction is initiated.Suitable viscosity modifiers include elastomers and the norbornene-typepolymers of the present invention. The viscosity modifiers can bedissolved in the polymerizable monomers of the invention to increase theviscosity of the monomer reaction mixture. As discussed above,crosslinking can be effected during the initial polymerization reactionof the monomer mixture or during a post polymerization thermal orphotochemical curing step.

When employed in the mass polymerization system of the invention, thepreferred molar ratio of monomer to procatalyst (based on metal content)to WCA salt activator ratios preferably ranges from about 500,000:1:1toabout 5,000:1:20, more preferably from about 250,000:1:5 to about20,000:1:10, and most preferably from about 200,000:1:20 to about100,000:1:1.

The polymers produced by the foregoing processes are useful inter aliain electronic and optical applications. In electronic applications usesinclude but are not limited to dielectric films (i.e., multichip modulesand flexible circuits), chip attach adhesives, underfill adhesives, chipencapsulants, glob tops, near hermetic board and chip protectivecoatings, embedded passives, laminating adhesives, capacitordielectrics, high frequency insulator/connectors, high voltageinsulators, high temperature wire coatings, conductive adhesives,reworkable adhesives, photosensitive adhesives and dielectric film,resistors, inductors, capacitors, antennas and printed circuit boardsubstrates. In optical applications uses include but are not limited tooptical films, ophthalmic lenses, wave guides, optical fiber,photosensitive optical film, specialty lenses, windows, high refractiveindex film, laser optics, color filters, optical adhesives, and opticalconnectors.

Due to the high activity of the Group 10 catalysts of the presentinvention, the amount of Group 10 residual metal in the polymer product(absent any purification) is preferably less than about 100 ppm, morepreferably less than about 50 ppm, even more preferably less than 10ppm, and most preferably less than 5 ppm, wherein the residual metal topolymer is calculated on a weight to weight basis.

The following examples are detailed descriptions of methods ofpreparation and use of certain compositions of the present invention.The detailed preparation descriptions fall within the scope of, andserve to exemplify, the more generally described methods set forthabove.

The examples are presented for illustrative purposes only, and are notintended as a restriction on the scope of the invention.

EXAMPLE 1 Procatalyst A.(Allyl)palladium(tricyclohexylphosphine)chloride

To (allyl)palladium chloride dimer (1.00 g, 2.73 mmol) was added about75 ml of toluene to give a yellow solution with a small amount ofinsolubles. To this mixture was added tricyclohexylphosphine (1.55 g,5.54 mmol) dissolved in about 20 ml of toluene. A clear yellow solutionresulted which was allowed to stir at room temperature for 2 hours. Thesolvent was removed in vacuo to yield a pale yellow powder which wasdissolved in THF and stirred overnight. The THF was then removed invacuo to give an off-white powder which was washed with 50 ml of etherthree times. The resulting free-flowing, off-white powder was dried invacuo. Yield 1.6 g (63%). ³¹P NMR (CD₂Cl₂): δ 41.1 (s). ¹H NMR (CD₂Cl₂):δ 5.40 (m, 1H), 4.49 (br t, 1H), 3.49 (d of d, 1H), 3.42 (s, 1H), 2.59(d, 1H), 2.14 (m, 3H), 1.90 (br s, 6H), 1.80 (s, 6H), 1.72 (s, 3H), 1.47(br s, 6H), 1.27 (s, 9H).

EXAMPLE 2 Procatalyst B.(Allyl)palladium(tricyclohexylphosphine)triflate

A methylene chloride solution of(allyl)palladium(tricyclohexylphosphine)chloride (1.00 g, 2.16 mmol) wasadded to a methylene chloride solution of silver triflate (0.565 g, 2.20mmol). The reaction mixture was shielded from room light and allowed tostir for 18 hours. The resulting slurry was filtered to yield a lightyellow filtrate. The methylene chloride was removed in vacuo to give afree-flowing white powder. Yield 1.05 g (84%). ³¹P NMR (C₆D₆): 42.2 (s).¹H NMR (C₆D₆): δ 5.10 (t, 1H), 4.66 (m, 1H), 3.64 (d of d, 1H), 2.62 (s,1H), 1.95 (d, 1H), and peaks from 1.9 to 1.0 due totricyclohexylphosphine. Crystals of this material were grown frommethylene chloride/pentane solution. The results of a x-ray crystalstructure determination are presented in FIG. 1.

EXAMPLE 3 (Allyl)palladium Trifluoroacetate Dimer

Approximately 1.60 g (4.34 mmol) of (allyl)palladium chloride dimer wasdissolved in methylene chloride. This solution was added to a methylenechloride solution of silver trifluoroacetate 2.02 g (9.14 mmol) whichwas cooled to −10° C. The mixture was allowed to stir for 3 hours. Theresulting cloudy solution was filtered to yield a bright, yellowfiltrate. Removal of solvent in vacuo gave a yellow powder. ¹H NMR(CD₂Cl₂): δ 5.63 (br s, 1H), 4.13 (d, 2H), 3.08 (d, 2H).

EXAMPLE 4 Procatalyst C.(Allyl)palladium(tricyclohexylphosphine)trifluoroacetate

(Allyl)palladium trifluoroacetate dimer (1.00 g, 1.91 mmol) wasdissolved in THF at −78° C. To this solution was addedtricyclohexylphosphine (1.12 g, 4.00 mmol) in THF. The yellow solutionbecame colorless. After 20 minutes the solution was allowed to warm toroom temperature and stir for 2 hours. The solvent was removed in vacuoto give an off-white powder. Yield 0.96 g (47%). ³¹P NMR (CD₂Cl₂): δ41.7 (s). ¹H NMR (CD₂Cl₂): δ 5.47 (m, 1H), 4.78 (t, 1H), 3.82 (d of d,1H), 3.24 (s, 1H), 2.50 (d, 1H), and peaks from 1.9 to 1.0 due totricyclohexylphosphine.

EXAMPLE 5 Procatalyst D.{2-[(Dimethylamino)methyl]phenyl-C,N-}palladium(tricyclohexylphosphine)chloride

Di-μ-chlorobis{2-[(dimethylamino)methyl]phenyl-C,N-}dipalladium (1.00 g,1.81 mmol) was dissolved in THF (60 ml). To this solution was addedtricyclohexylphosphine (1.00, 3.57 mmol) in 10 ml of THF. The mixturewas allowed to stir overnight after which the solvents were removed invacuo. The resulting solid was dissolved in methylene chloride andallowed to stir for 1 hour. The solvent was removed in vacuo. To thesolid was added an 80:20 mixture of pentane:ether. The solvent wasdecanted. To this solid was added cyclohexane followed by filtration toyield a white solid which was dried in vacuo. Yield 0.96 g (48%). ³¹PNMR (CD₂Cl₂): δ 43.4 (s). ¹H NMR (CD₂Cl₂): δ 7.22 (m, 1H), 6.98 (d, 1H),6.90 (m, 2H), 3.93 (s, 2H), 2.58 (d, 6H), and peaks from 2.4 to 1.0 dueto tricyclohexylphosphine.

EXAMPLE 6 Procatalyst E.{2-[(Dimethylamino)methyl]phenyl-C,N-}palladium(tricyclohexylphosphine)triflate

{2-[(dimethylamino)methyl]phenyl-C,N-}palladium(tricyclohexylphosphine)chloride(0.500 g, 0.899 mmol) was dissolved in fluorobenzene. To this solutionwas added silver triflate (0.231 g, 0.899 mmol) in a fluorobenzene/ethersolution. The reaction mixture turned yellow with precipitation of awhite solid. The mixture was allowed to stir for 64 hours. The whitesolid was filtered off and the solvent was removed in vacuo from theyellow filtrate to give a white solid. ³¹P NMR (CD₂Cl₂): δ 42.1 (s).

EXAMPLE 7 Procatalyst F. (Allyl)palladium(tri-o-tolylphosphine)chloride

To (allyl)palladium chloride dimer (1.50 g, 4.10 mmol) solution in about25 ml of methylene chloride was added tri-o-tolylphosphine (2.50 g, 8.22mmol) as a methylene chloride solution. The solution was allowed to stirovernight. The solvent was removed in vacuo to yield a pale yellowpowder. Yield 3.50 g (88%). ³¹P NMR (CD₂Cl₂): δ 21.4 (s). ¹H NMR(CD₂Cl₂): δ 7.58 (br t, 3H), 7.40 (t, 3H), 7.24 (m, 6H), 5.60 (m, 1H),4.57 (t, 1H), 3.55 (d of d, 1H), 3.16 (br s, 1H), 2.19 (s, 9H).

EXAMPLE 8 Procatalyst G. (Allyl)palladium(tri-o-tolylphosphine)triflate

To a methylene chloride solution (10 ml) of (allyl)palladium chloridedimer (1.50 g, 4.10 mmol) was added a methylene chloride solution (10ml) of tri-o-tolylphosphine (2.50 g, 8.22 mmol). This solution was addedto a methylene chloride solution of silver triflate (1.81 g, 8.19 mmol).A precipitate formed immediately. The reaction mixture was shielded fromroom light and allowed to stir overnight. The resulting slurry wasfiltered through Celite® to yield an orange filtrate. The methylenechloride was. removed in vacuo to give a yellow powder which was washedwith pentane twice, an 80:20 mixture of pentane:ether, then dried invacuo. Yield 4.05 g (91%). ³¹P NMR (CD₂Cl₂): 21.4 (s). ¹H NMR (CD₂Cl₂):δ 7.44 (m, 6H), 7.26 (m, 6H), 5.70 (br s, 1H), 5.10 (br s, 1H), 3.95 (brs, 1H), 3.20 (br s, 1H), 2.37 (br s, 1H), 2.19 (s, 9H). Crystals of thismaterial were grown from methylene chloride/pentane solution. Theresults of a x-ray crystal structure determination are presented in FIG.2.

EXAMPLE 9 Procatalyst H. (Allyl)palladium(tri-o-tolylphosphine)nitrate

To a suspension of silver nitrate (0.935 g, 5.50 mmol) in methylenechloride was added a methylene chloride solution of (allyl)palladiumchloride dimer (1.00 g, 2.73 mmol) and tri-o-tolylphosphine (1.66 g,5.46 mmol). After stirring the mixture overnight, the mixture wasfiltered to give an orange filtrate. This solution was concentrated andlayered with pentane. The resulting white solid was isolated. ³¹P NMR(CD₂Cl₂): 20.3 (s). ¹H NMR (CD₂Cl₂): δ 7.50-7.20 (m, 12H), 5.70 (m, 1H),4.85 (t, 1H), 3.95 (d of d, 1H), 2.60 (br s, 2H), 2.20 (s, 9H).

EXAMPLE 10 Procatalyst I. (Allyl)palladium(tri-o-tolylphosphine)acetate

To a suspension of silver acetate (0.919 g, 5.50 mmol) in methylenechloride was added a methylene chloride solution of (allyl)palladiumchloride dimer (1.00 g, 2.73 mmol) and tri-o-tolylphosphine (1.66 g,5.46 mmol). After stirring the mixture overnight, the mixture wasfiltered to give an orange filtrate. This solution was concentrated andlayered with pentane. The resulting white solid was isolated. ³¹P NMR(CD₂Cl₂): 20.8 (s). ¹H NMR (CD₂Cl₂): δ 7.50-7.20 (m, 12H), 5.60 (m, 1H),4.67 (t, 1H), 3.80 (d of d, 1H), 2.50 (br s, 2H), 2.20 (s, 9H).

EXAMPLE 11 Procatalyst J. (β-pinenyl)palladium Chloride Dimer

To a slurry of palladium (II) trifluoroacetate (0.5 g, 1.5 mmol) inacetone was added β-pinene (0.23 ml, 1.5 mmol). After 45 minutes, NBu₄Cl(0.460 g, 1.65 mmol) in acetone was added and the reaction mixture wasstirred for 10 minutes. Some black solid was filtered off and thesolvent was removed in vacuo. The solid residue was dissolved inchloroform. Addition of pentane gave a brown oil and a yellow solution.From the yellow solution a yellow solid was obtained by removal ofsolvent in vacuo. Yield 0.2 g.

EXAMPLE 12 Procatalyst K. (Allyl)palladium Iodide Dimer

(Allyl)palladium chloride dimer (1.0 g, 2.7 mmol) was dissolved inacetone (25 ml). To this solution was added an aqueous solution (10 ml)of sodium iodide (2.0 g, 13.3 mmol). The solution immediately turnedorange and a yellow solid formed. The mixture was stirred for 30 minutesand solution was isolated by decantation. The solvent was removed invacuo to give a solid which was extracted with chloroform. Thechloroform extract was dried in vacuo to give an orange-brown solid.Yield 0.66 g (44%). ¹H NMR (C₆D₆): δ 4.32 (m, 1H), 3.78 (d, 2H), 2.40(d, 2H). A peak was observed at 548 by FD-MS with the expected isotopepattern for two palladium and two iodine atoms.

EXAMPLE 13 Catalyst L.(Allyl)palladium(tricyclohexylphosphine)(ether)][tetrakis(bis(3,5-trifluoromethyl)phenyl)borate]

(Allyl)palladium(tricyclohexylphosphine)chloride (1.00 g, 2.73 mmol) wasdissolved in ether and cooled to −78° C. Methylmagnesium bromide (720 μlof 3 m solution in ether, 2.16 mmol) was added drop wise. The mixturewas stirred at −78° C. for 1 hour after which the solvent was removed invacuo. The solid was extracted twice with pentane and filtered. Thesolution was stored at −20° C. overnight. A precipitate formed and theflask was further cooled to −78° C. The resulting solid was collectedand dried. Yield 0.5 g (52%). NMR spectra are in agreement with theformation of (allyl)palladium(tricyclohexylphosphine)(methyl). ³¹P NMR(CD₂Cl₂): δ 42.3 (s). ¹H NMR (CD₂Cl₂): δ 4.99 (m, 1H), 3.45 (d, 1H),3.31 (br t, 1H), 2.39 (d of d, 1H), 2.33 (d, 1H), 2.00 (m, 3H), 1.86 (brs, 6H), 1.78 (br s, 6H), 1.71 (s, 3H), 1.39 (br s, 6H), 1.24 (br s, 9H).

A flask was charged with(allyl)palladium(tricyclohexylphosphine)(methyl) (0.26 g, 0.58 mmol) andH(Et₂O)₂[tetrakis(bis(3,5-trifluoromethyl)phenyl)borate] (0.59 g, 0.58mmol). The contents of the flask were cooled to −78° C. and 15 ml ofether was added. The mixture was warmed slightly to facilitatedissolution and then cooled to −78° C. After stirring for 3 hours, thesolvent was removed in vacuo to give a brown-yellow solid. After washingwith pentane twice and drying in vacuo a beige crystalline solid wasisolated. Yield 0.69 g (87%). ³¹P NMR (CD₂Cl₂): δ 43.1 (s). ¹H NMR(CD₂Cl₂): δ 7.72 (s, 8H), 7.56 (s, 4H), 5.83 (br m, 1H), 5.15 (br s,1H), 4.05 (br s, 1H), 3.95 (br s, 1H), 3.44 (q, 4H), 3.20 (br s, 1H),1.16 (t, 6H), and peaks from 2.05 to 1.1 due to tricyclohexylphosphine.

EXAMPLE 14 Procatalyst M.{2-[1-(dimethylamino)ethyl]phenyl-C,N-}palladium(tricyclohexylphosphine)chloride

(+)-Di-μ-chlorobis{2-[1-(dimethylamino)ethyl]phenyl-C,N-}dipalladium(0.65 g, 1.1 mmol) was dissolved in methylene chloride. To this solutionwas added 10 ml of a methylene chloride solution oftricyclohexylphosphine (0.63 g, 2.2 mmol). After 10 hours, the solventwas removed in vacuo. To the yellow residue was added pentane. Theyellow pentane solution was decanted from some insolubles. Then thepentane was pumped off from the solution to give a light yellow powder.³¹P NMR (CD₂Cl₂): δ 41.8 (s). ¹H NMR (CD₂Cl₂): δ 7.22 (m, 1H), 6.93 (m,2H), 6.86 (m, 1H), 3.65 (m, 1H), 2.55 (d, 6H), 1.75 (d, 1H), and peaksfrom 2.5 to 1.1 due to tricyclohexylphosphine.

EXAMPLE 15 Procatalyst N. Preparation ofbis(Tricyclohexylphosphine)(hydrido)palladium(II)chloride

To a slurry of (1,5-cyclooctadiene)palladium(II)chloride (2.0 g) in 20ml methanol was added 1.67 g of a 25 wt. % solution of sodium methoxidein methanol diluted with 20 ml methanol. After 0.5 hours,(2-methoxy-3-cyclooctenyl)palladium chloride dimer was isolated as awhite powder by filtration in air and dried under vacuum (1.67 g, 85%).

To a slurry of (2-methoxy-3-cyclooctenyl)palladium chloride dimer (500mg) in 25 ml methanol was added tricyclohexylphosphine (1.0 g) as asolid. The reaction was stirred until it became homogeneous. Stirringwas stopped and the solution was cooled in a −20° C. freezer. Theproduct was isolated as a gray crystalline solid by filtration in airand dried under vacuum (900 mg, 72%).

EXAMPLE 16 Catalyst 0. Preparation ofbis(Tricyclohexylphosphine)(hydrido)palladium(II)nitrate

To a slurry of tricyclohexylphosphine (4.86 g) in 75 ml ethanol wasadded palladium(II)nitrate (2.0 g) as a solid at −35° C. A yellowprecipitate formed immediately. After 1.5 hours, toluene (150 ml) wasadded and the reaction warmed to −5° C. Sodium borohydride (0.33 g) wasadded in 25 ml ethanol, and the reaction was allowed to warm to roomtemperature. After 40 hours, the reaction was filtered and the solventremoved to give a tan solid. The product was washed with 75 ml ethylether and several times with hexane. Recrystallization fromtoluene/hexane gave the product as tan crystals (3.3 g, 53%).

EXAMPLE 17 Catalyst P. Synthesis of (Allyl)platinum Chloride Tetramer

(Allyl)platinum chloride tetramer was synthesized according to J. Lukasin Inorganic Synthesis 1974, 15, 79.

EXAMPLE 18 Procatalyst Q. Synthesis of(Methallyl)nickel(tricyclohexylphosphine)(triflate)

(Methallyl)nickelchloride dimer (2.0 g, 0.0066 mmol) was added to aflask along with tricyclohexylphosphine (3.42 g, 0.0133 mmol). Methylenechloride (25 ml) was added to the flask to give an orange-yellowsolution. Silver triflate (3.72 g, 0.0133 mmol) was mixed with methylenechloride (10 ml) in an amber vial. The nickel solution was added to thesilver mixture. Immediate precipitation of silver chloride was noted.The mixture was allowed to stir for 3 hours at room temperature. Themixture was filtered through Celite® to give an orange-yellow filtrate.The solvent was removed in vacuo to give a yellow solid. Yield 5.44 g(75%). ³¹P NMR (CDCl₃): δ 33.2 (s). ¹H NMR (CDCl₃): δ 4.49 (s, 1H), 3.19(s, 1H), 2.24 (s, 3H), 2.11 (s, 1H), and peaks from 2.0 to 1.1 due totricyclohexylphosphine.

EXAMPLE 19 Procatalyst R. Synthesis of(Allyl)platinum(tricyclohexylphosphine)(chloride)

(Allyl)platinum chloride tetramer (0.20 g, 0.18 mmol) was suspended in25 ml of methylene chloride. Tricyclohexylphosphine (0.21 g, 0.74 mmol)was dissolved in methylene chloride and added to the platinum solution.A yellow solution resulted with some insolubles. The mixture was allowedto stir for 2 days. A tan solution and solid resulted. The volatileswere pumped away to give a tan solid. Yield 0.25 g (63%).

EXAMPLE 20 Procatalyst S. Synthesis of(Allyl)platinum(tricyclohexylphosphine)(triflate)

(Allyl)platinum(tricyclohexylphosphine)(chloride) (0.25 g, 0.45 mmol)was dissolved in toluene and filtered to remove small amount ofinsolubles. The resulting filtrate was added to a toluene slurry ofsilver triflate (0.11 g, 0.45 mmol). The mixture was stirred for 2hours, then filtered to give a yellow filtrate. The solvent was removedin vacuo to give a tan solid.

EXAMPLE 21 Procatalyst T. Synthesis of(Allyl)palladium(trinaphthylphosphine)(triflate)

Trinaphthylphosphine (1.6 g, 3.5 mmol, 90%) and (allyl)palladiumchloride dimer (0.61 g, 1.7 mmol) were added to a flask that was cooledto −10° C. To this mixture was added methylene chloride (25 ml)drop-wise to give a light yellow mixture. The slurry was warmed at roomwith stirring. The mixture turned orange-brown. After 6 hours, thesolution was added to a suspension of silver triflate (0.85 g, 3.3 mmol)in 25 ml of methylene chloride. A white precipitate formed. After 16hours the mixture was filtered. The filtrate was pumped to drynessgiving a brown solid. Yield 2.3 g (96%). The solid was recrystallizedfrom methylene chloride/pentane. ³¹P NMR (CDCl₃): δ 20.7 (br s). ¹H NMR(CDCl₃): δ 8.3-7.3 (m, 21H), 5.54 (br s, 1H), 5.18 (br t, 1H), 3.91 (m,1H), 3.03 (br s, 1H), 2.25 (br s, 1H). Crystals of this material weregrown from methylene chloride/pentane solution. The results of a x-raycrystal structure determination are presented in FIG. 3.

EXAMPLE 22 Procatalyst U. A Suspension of(Allyl)palladium(trinaphthylphosphine)(triflate)

(0.50 g, 0.70 mmol) in 100 ml of toluene was added to a slurry ofether-free lithium tetrakis(pentafluorophenyl)borate (0.48 g, 0.70 mmol)in toluene. After stirring the mixture for 30 minutes, the solution wasfiltered through Celite® to give a yellow filtrate. The solution wasconcentrated in vacuo and layered with pentane to give an orange oil.The solvent was decanted and the oil was washed with pentane and thendried in vacuo and then washed twice more with pentane and dried to givean light orange solid.

EXAMPLE 23

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0006 mmol). Thismixture was diluted with 38 ml of toluene. Approximately 10 μl of atoluene solution of (allyl)palladium chloride dimer (6.23 mMol) and 10μl of a toluene solution of tricyclohexylphosphine (12.5 mMol) wasdiluted to about 1 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was poured into acetone to precipitate the polymer whichwas redissolved into toluene and reprecipitated into methanol which wasfiltered and dried in vacuo overnight. Yield 6.2 g (62%).

EXAMPLE 24

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate 2.5 Et₂O (0.6 mg, 0.0006 mmol). Thismixture was diluted with 38 ml of toluene. Approximately 10 μl of atoluene solution of (allyl)palladium chloride dimer (6.23 mMol) and 50μl of a toluene solution of tricyclohexylphosphine (12.5 mMol) wasdiluted to about 1 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was poured into acetone to precipitate the polymer whichwas redissolved into toluene and reprecipitated into methanol which wasfiltered and dried in vacuo overnight. Yield 6.4 g (64%).

EXAMPLE 25

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.2 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.3 mg, 0.0004 mmol). Thismixture was diluted with 38 ml of toluene. Approximately 10 μl of atoluene solution of (allyl)palladium chloride dimer (6.23 mMol) and 10μl of a toluene solution of tricyclohexylphosphine (12.5 mMol) wasdiluted to about 1 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was poured into acetone to precipitate the polymer whichwas redissolved into toluene and reprecipitated into methanol, filteredand dried in vacuo overnight. Yield 6.1 g (61%).

EXAMPLE 26

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.1 mg, 0.00006 mmol). Thismixture was diluted with 38 ml of toluene. Approximately 10 μl of atoluene solution of (allyl)palladium chloride dimer (6.23 mMol) and 10μl of a toluene solution of tricyclohexylphosphine (12.5 mMol) wasdiluted to about 1 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was poured into acetone to precipitate the polymer whichwas redissolved into toluene and reprecipitated into methanol, filteredand dried in vacuo overnight. Yield 2.4 g (24%).

EXAMPLE 27 Comparative

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrafluoroborate (0.1 mg, 0.0006 mmol). This mixture was diluted with38 ml of toluene. Approximately 10 μl of a toluene solution of(allyl)palladium chloride dimer (6.23 mMol) and 10 μl of a toluenesolution of tricyclohexylphosphine (12.5 mMol) was diluted to about 1 mltotal with toluene and added to the monomer solution. The mixture washeated to 65° C. for 4 hours. The solution did not become viscous and,upon addition to acetone, no polymer was observed.

EXAMPLE 28

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate 2.5 Et₂O (1.1 mg, 0.0013 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 20 μl of atoluene solution of (allyl)palladium chloride dimer (0.623 mMol) and 20μl of a toluene solution of triphenylphosphine (12.5 mMol) was dilutedto about 1 ml total with toluene and added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting viscous mixturewas poured into acetone to precipitate the polymer which was filteredand dried in vacuo overnight. Yield 5.2 g (52%).

EXAMPLE 29

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0012 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 10 μl of atoluene solution of (allyl)palladium chloride dimer (12.5 mMol) and 20μl of a toluene solution of tricyclohexylphosphine (12.5 mMol) wasdiluted to about 1 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was diluted with toluene and poured into methanol toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 8.2 g (82%).

EXAMPLE 30

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0012 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 80 μl of atoluene solution of (allyl)palladium trifluoroacetate dimer (1.6 mMol)and 20 μl of a toluene solution of tricyclohexylphosphine (12.5 mMol)was diluted to about 1 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was diluted with toluene and poured into methanol toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 9.3 g (93%).

EXAMPLE 31

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0012 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 40 μl of atoluene solution of (allyl)palladium trifluoroacetate dimer (1.6 mMol)and 20 μl of a toluene solution of tricyclohexylphosphine (12.5 mMol)was diluted to about 1 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was diluted with toluene and poured into methanol toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 8.3 g (83%).

EXAMPLE 32

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0012 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 20 μl of atoluene solution of (allyl)palladium trifluoroacetate dimer (1.6 mMol)and 20 μl of a toluene solution of tricyclohexylphosphine (12.5 mMol)was diluted to about 1 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was diluted with toluene and poured into methanol toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 3.9 g (39%).

EXAMPLE 33

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0012 mmol). Thismixture was diluted with 24 ml of toluene and 8 ml of ethanol.Approximately 0.1 mg (0.0003 mmol) of(allyl)palladium(tricyclohexylphosphine) chloride (Catalyst A) to about1 ml total with toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was diluted withtoluene and poured into methanol to precipitate the polymer which wasfiltered and dried in vacuo overnight. Yield 0.72 g (7.2%).

EXAMPLE 34

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0012 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 0.1 mg (0.0003mmol) of (allyl)palladium(tricyclohexylphosphine)chloride (Catalyst A)to about 1 ml total with toluene and added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting viscous mixturewas diluted with toluene and poured into methanol to precipitate thepolymer which was filtered and dried in vacuo overnight. Yield 7.8 g(78%).

EXAMPLE 35

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0012 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 50 μl of atoluene solution of (allyl)palladium chloride dimer (2.5 mMol) and 20 μlof a toluene solution of tribenzylphosphine (12.5 mMol) was diluted toabout 1 ml total with toluene and added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting viscous mixturewas diluted with toluene and poured into acetone to precipitate thepolymer which was filtered and dried in vacuo overnight. Yield 2.1 g(21%).

EXAMPLE 36

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0012 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 50 μl of atoluene solution of (allyl)palladium chloride dimer (2.5 mMol) and 20 μlof a toluene solution of tributylphosphine (12.5 mMol) was diluted toabout 1 ml total with toluene and added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting viscous mixturewas diluted with toluene and poured into acetone to precipitate thepolymer which was filtered and dried in vacuo overnight. Yield 4.1 g(41%).

EXAMPLE 37

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added sodiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate (1.1 mg, 0.0004 mmol).This mixture was diluted with 32 ml of toluene. Approximately 50 μl of atoluene solution of (allyl)palladium chloride dimer (2.5 mMol) and 20 μlof a toluene solution of tricyclohexylphosphine (12.5 mMol) was dilutedto about 1 ml total with toluene and added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting viscous mixturewas diluted with toluene and poured into acetone to precipitate thepolymer which was filtered and dried in vacuo overnight. Yield 9.3 g(93%).

EXAMPLE 38

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added trityltetrakis(pentafluorophenyl)borate (1.1 mg, 0.0012 mmol). This mixturewas diluted with 32 ml of toluene. Approximately 50 μl of a toluenesolution of (allyl)palladium chloride dimer (2.5 mMol) and 20 μl of atoluene solution of tricyclohexylphosphine (12.5 mMol) was diluted toabout 1 ml total with toluene and added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting viscous mixturewas diluted with toluene and poured into acetone to precipitate thepolymer which was filtered and dried in vacuo overnight. Yield 1.0 g(10%).

EXAMPLE 39

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0007 mmol). Thismixture was diluted with 16 ml of toluene. Approximately 20 μl of atoluene solution of{2-[(dimethylamino)methyl]phenyl-C,N-}palladium(tricyclohexylphosphine)chloride(Catalyst D, 6.52 mMol) was added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting viscous mixture wasdiluted with toluene and poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 3.8 g (76%).

EXAMPLE 40

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0007 mmol). Thismixture was diluted with 16 ml of toluene. Approximately 20 μl of atoluene solution of{2-[(dimethylamino)methyl]-phenyl-C,N-}palladium(tricyclohexylphosphine)triflate(Catalyst E, 6.52 mMol) was added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting viscous mixture wasdiluted with toluene and poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 5.0 g (100%).

EXAMPLE 41

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0007 mmol). Thismixture was diluted with 16 ml of toluene. Approximately 10 μl of atoluene solution of (allyl)palladium chloride dimer (3.26 mMol) and 10μl of a toluene solution of triallylphosphine (6.52 mMol) was diluted toabout 3 ml total with toluene and added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting viscous mixturewas diluted with toluene and poured into methanol to precipitate thepolymer which was filtered and dried in vacuo overnight. Yield 1.6 g(32%). Mw=2,460,000 and Mn=1,230,000 as determined by GPC methods.

EXAMPLE 42

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0007 mmol). Thismixture was diluted with 16 ml of toluene. Approximately 10 μl of atoluene solution of (allyl)palladium chloride dimer (3.26 mMol) and 10μl of a toluene solution of tricyclopentylphosphine (6.52 mMol) wasdiluted to about 3 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was diluted with toluene and poured into methanol toprecipitate the polymer, filtered and dried in vacuo overnight. Yield4.8 g (96%).

EXAMPLE 43

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0007 mmol). Thismixture was diluted with 16 ml of toluene. Approximately 10 μl of atoluene solution of (allyl)palladium chloride dimer (3.26 mMol) and 10μl of a toluene solution of triisopropylphosphite (6.52 mMol) wasdiluted to about 3 ml total with toluene and added to the monomersolution. The mixture was heated to 65° C. for 4 hours. The resultingviscous mixture was diluted with toluene and poured into methanol toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 0.2 g (4%).

EXAMPLE 44

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis{tris(trifluoromethyl)-tert-butoxy}aluminate (1.1 mg, 0.0011mmol). This mixture was diluted with 16 ml of toluene. Approximately 200μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (1.08 mMol) was addedto the monomer solution. The mixture was heated to 65° C. for 4 hours.The resulting viscous mixture was diluted with toluene and poured intomethanol to precipitate the polymer which was filtered and dried invacuo overnight. Yield 5 g (100%).

EXAMPLE 45

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added thefluorinated tetraalkoxyaluminate, Li[Al(OC(CF₃)₃)₄] (1.1 mg, 0.0011mmol). This mixture was diluted with 16 ml of toluene. Approximately 200μl of a toluene solution of{2-(dimethylamino)methyl]-phenyl-C,N-}palladium(tricyclohexylphosphine)triflate(Catalyst E, 1.08 mMol) was added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting viscous mixture wasdiluted with toluene and poured into methanol to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 5 g (100%).

EXAMPLE 46

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added thefluorinated tetraalkoxyaluminate, Li[Al(OC(CF₃)₂Ph)₄] (1.1 mg, 0.0011mmol). This mixture was diluted with 32 ml of toluene. Approximately 100μl of a toluene solution of{2-(dimethylamino)methyl]-phenyl-C,N-}palladium(tricyclohexylphosphine)triflate(Catalyst E, 2.16 mMol) was added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting viscous mixture wasdiluted with toluene and poured into methanol to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 4.6 g (92%).

EXAMPLE 47

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added thefluorinated carborane salt, LiCB₁₁F₁₁H (0.4 mg, 0.001 mmol). Thismixture was diluted with 32 ml of toluene. Approximately 100 μl of atoluene solution of{2-(dimethylamino)methyl]-phenyl-C,N-}palladium(tricyclohexylphosphine)triflate(Catalyst E, 2.16 mMol) was added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting viscous mixture wasdiluted with toluene and poured into methanol to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 2.7 g (54%).

EXAMPLE 48

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added the brominatedcarborane salt, LiCB₁₁H₆Br₆ (0.7 mg, 0.001 mmol). This mixture wasdiluted with 32 ml of toluene. Approximately 100 μL of a toluenesolution of{2-(dimethylamino)methyl]-phenyl-C,N-}palladium(tricyclohexylphosphine)triflate(Catalyst E, 2.16 mMol) was added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting viscous mixture wasdiluted with toluene and poured into methanol to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 1.5 g (31%).Mw=417,000 and Mn=212,000 as determined by GPC methods.

EXAMPLE 49

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0006 mmol). Thismixture was diluted with 38 ml of toluene. Approximately 20 μl of atoluene solution of (allyl)palladium chloride dimer (3.28 mMol) and 20μl of a toluene solution of trifurylphosphine (6.57 mMol) was dilutedwith toluene and added to the monomer solution. The mixture was heatedto 65° C. for 4 hours. The resulting viscous mixture was poured intoacetone to precipitate the polymer which was redissolved into tolueneand reprecipitated into methanol which was filtered and dried in vacuoovernight. Yield 1.9 g (37%).

EXAMPLE 50

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0006 mmol). Thismixture was diluted with 38 ml of toluene. Approximately 20 μl of atoluene solution of (allyl)palladium chloride dimer (3.28 mMol) and 20μl of a toluene solution of tri-m-methoxyphenylphosphine (6.57 mMol) wasdiluted with toluene and added to the monomer solution. The mixture washeated to 65° C. for 4 hours. The resulting viscous mixture was pouredinto acetone to precipitate the polymer which was redissolved intotoluene and reprecipitated into methanol which was filtered and dried invacuo overnight. Yield 0.5 g (10%).

EXAMPLE 51

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0006 mmol). Thismixture was diluted with 38 ml of toluene. Approximately 20 μl of atoluene solution of (allyl)palladium chloride dimer (3.28 mMol) and 20μl of a toluene solution of tri-p-methoxyphosphine (6.57 mMol) wasdiluted with toluene and added to the monomer solution. The mixture washeated to 65° C. for 4 hours. The resulting viscous mixture was pouredinto acetone to precipitate the polymer which was redissolved intotoluene and reprecipitated into methanol which was filtered and dried invacuo overnight. Yield 3.6 g (72%).

EXAMPLE 52

To a clean, dry 500 ml stainless steel reactor was added 45.8 gbutylnorbornene (305 mmol) and 4.2 g of 5-triethoxysilylnorbornene (16.4mmol) diluted with toluene to a total volume of 320 ml. The mixture washeated to 65° C. with agitation. To this mixture was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (9.4 mg, 0.011 mmol) in 4 mlof toluene. Approximately 1.3 mg of(allyl)palladium(tri-o-tolylphosphine)triflate (Catalyst G, 0.0022 mmol)in 3 ml of toluene was added to the reactor. After 4 hours the reactionmixture was poured into acetone to precipitate the polymer which wasfiltered and dried in vacuo overnight. Yield 16.2 g (33%). Mw=165,000and Mn=71,000 as determined by GPC methods.

EXAMPLE 53

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.00011 mmol). Thismixture was diluted with 16 ml of toluene. Approximately 100 μl of atoluene solution oftrans-di-(μ-acetato)-bis[o-(di-o-tolylphosphino)benzyl]dipalladium (1.1mMol) and 100 μl of a toluene solution of tricyclohexylphosphine (2.1mMol) was diluted with a small amount of toluene and was added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting mixture was diluted with toluene and poured into methanol toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 5 g (100%).

EXAMPLE 54

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.00011 mmol) andtriphenylphosphine supported on 20% crosslinked polystyrene (0.71 mg,0.8 weight percent phosphorus) This mixture was diluted with 16 ml oftoluene. Approximately 100 μl of a toluene solution of allylpalladiumchloride dimer (1.1 mMol) was added to the mixture. The mixture washeated to 65° C. After 4 hours the mixture was poured into an excess ofacetone to precipitate the polymer which was filtered and dried invacuo. Yield 0.15 g (3%).

EXAMPLE 55

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was addedN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1.0 mg, 0.00011mmol). This mixture was diluted with 16 ml of toluene. Approximately 100μl of a toluene solution (1,5-cyclooctadiene)(dimethyl)platinum (2.3mMol) and 200 μl of a toluene solution of tricyclohexylphosphine (2.1mMol) was diluted with a small amount of toluene and was added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting mixture was diluted with toluene and poured into methanol toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 0.11 g (2%).

EXAMPLE 56 Comparative

A mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was diluted with 16 mlof toluene. A solution of (allyl)palladium chloride dimer (0.00011 mmol)and tricyclohexylphosphine (0.00022 mmol) in toluene was added to themonomer solution. No WCA salt activator was employed. The mixture washeated to 65° C. for 4 hours. The mixture was then poured into an excessof acetone. No polymer precipitated.

EXAMPLE 57 Comparative

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol). Thismixture was diluted with 16 ml of toluene. A solution of(allyl)palladium chloride dimer (0.00011 mmol) in toluene was added tothe monomer solution. No neutral Group 15 electron donor ligandproviding compound was added. The mixture was heated to 65° C. for 4hours. The mixture was then poured into an excess of acetone. No polymerprecipitated.

EXAMPLE 58

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol). Thismixture was diluted with 16 ml of toluene. A solution of(allyl)palladium chloride dimer (0.00011 mmol) andtricyclohexylphosphine (0.00022 mmol) in toluene was added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting viscous mixture was diluted in toluene then poured into anexcess of acetone to precipitate the polymer. The polymer was filteredand dried in vacuo. Yield 4.25 g (85%).

EXAMPLE 59

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol). Thismixture was diluted with 16 ml of toluene. Approximately 100 μl of atoluene solution of{2-[1-(dimethylamino)-ethyl]phenyl-C,N-}palladium(tricyclohexylphosphinechloride (Catalyst M, 1.1 mMol) was added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting viscous mixturewas diluted with toluene and poured into acetone to precipitate thepolymer which was filtered and dried in vacuo overnight. Yield 5.0 g(100%).

EXAMPLE 60

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol) and5-butenylnorbornene (0.060 g, 0.00033 mol) as a chain transfer agent andcomonomer. The mixture was diluted with 32 ml of toluene. To thissolution was added 100 μl of a toluene solution ofallylpalladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3 mMol).After heating the mixture for 4 hours at 65° C., the mixture was pouredinto an excess of acetone. The resulting polymer was filtered and driedin vacuo. Yield 3.9 g (77%). Mw=1,372,000 and Mn=427,000 as determinedby GPC methods.

EXAMPLE 61

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol) and5-butenylnorbornene (0.180 g, 0.0010 mol) as a chain transfer agent andcomonomer. The mixture was diluted with 32 ml of toluene. To thissolution was added 100 μL of a toluene solution ofallylpalladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3 mMol).After heating the mixture for 4 hours at 65° C., the mixture was pouredinto an excess of acetone. The resulting polymer was filtered and driedin vacuo. Yield 3.7 g (73%). Mw=750,000 and Mn=230,000 as determined byGPC methods.

EXAMPLE 62

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0007 mmol) and5-butenyl norbornene (0.30 g, 0.0017 mol) as a chain transfer agent andcomonomer. The mixture was diluted with 32 ml of toluene. To thissolution was added 100 μl of a toluene solution ofallylpalladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3 mMol).After heating the mixture for 4 hours at 65° C., the mixture was pouredinto an excess of acetone. The resulting polymer was filtered and driedin vacuo. Yield 3.5 g (70%). Mw=428,000 and Mn=121,000 as determined byGPC methods.

EXAMPLE 63

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.6 mg, 0.0007 mmol) and5-butenylnorbornene (1.01 g, 0.0058 mol) as a chain transfer agent andcomonomer. The mixture was diluted with 32 ml of toluene. Approximately100 μl of a toluene solution oftrans-di-(μ-acetato)-bis[o-(di-o-tolylphosphino)benzyl]dipalladium (1.3mMol) and 100 μl of a toluene solution of tricyclohexylphosphine (2.6mMol) was added to the monomer solution. After heating the mixture for 4hours at 65° C., the mixture was poured into an excess of acetone. Theresulting polymer was filtered and dried in vacuo. Yield 2.5 g (51%).Mw=180,000 and Mn=63,000 as determined by GPC methods.

EXAMPLE 64

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol). Thismixture was diluted with 32 ml of toluene. To this mixture was added 100μl of a toluene solution ofbis(tricyclohexyl-phosphine)palladiumhydridochloride (Catalyst N, 1.3mMol). The mixture was heated to 65° C. for 4 hours after which themixture became so viscous that it could not be stirred. The polymer wasprecipitated into acetone, filtered and dried in vacuo. Yield 3.0 g(61%).

EXAMPLE 65

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol). Thismixture was diluted with 32 ml of toluene. To this mixture was added 100μl of a toluene solution ofbis(tricyclohexylphosphine)palladiumhydridonitrate (Catalyst 0, 1.3mMol). The mixture was heated to 65° C. for 4 hours after which themixture became so viscous that it could not be stirred. The polymer wasprecipitated into acetone, filtered and dried in vacuo. Yield 5 g(100%).

EXAMPLE 66

To a mixture of norbornene (5.0 g, 53 mmol was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol). Thismixture was diluted with 16 ml of toluene. To this mixture was added 200μl of a toluene solution ofallylpalladium(tricyclohexylphosphine)triflate (Catalyst B, 0.27 mMol).The mixture was allowed to stir at room temperature for 18 hours. Afterprecipitation, filtering and drying a yield of 0.68 g of polymer wasobtained. Yield 14%.

EXAMPLE 67

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol) and5-butenylnorbornene (0.05 g, 0.00033 mol). This mixture was diluted with16 ml of toluene. To this mixture was added 50 μL of a toluene solutionof (allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 4.75 g of polymer was obtained. Yield 95%. Mw=2,115,000and Mn=608,000 as determined by GPC methods.

EXAMPLE 68

To a mixture of butyl norbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol) and5-butenylnorbornene (0.15 g, 0.0010 mol). This mixture was diluted with16 ml of toluene. To this mixture was added 50 μL of a toluene solutionof (allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 4.54 g of polymer was obtained. Yield 91%. Mw=973,000and Mn=146,000 as determined by GPC methods.

EXAMPLE 69

To a mixture of butyl norbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol) and5-butenylnorbornene (0.25 g, 0.0017 mol). This mixture was diluted with16 ml of toluene. To this mixture was added 50 μL of a toluene solutionof (allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 4.03 g of polymer was obtained. Yield 81%. Mw=690,000and Mn=120,000 as determined by GPC methods.

EXAMPLE 70

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol) and5-butenylnorbornene (0.54 g, 0.0036 mol). This mixture was diluted with16 ml of toluene. To this mixture was added 50 μl of a toluene solutionof (allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 3.91 g of polymer was obtained. Yield 78%. Mw=379,000and Mn=120,000 as determined by GPC methods. The polymer containedapproximately 5% 5 butenylnorbornene according to ¹H NMR analysis.

EXAMPLE 71

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol) and5-butenylnorbornene (1.21 g, 0.0082 mol). This mixture was diluted with16 ml of toluene. To this mixture was added 50 μl of a toluene solutionof (allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 3.70 g of polymer was obtained. Yield 74%. Mw=202,000and Mn=68,000 as determined by GPC methods. The polymer containedapproximately 12% 5-butenylnorbornene according to ¹H NMR analysis.

EXAMPLE 72

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.0 mg, 0.0011 mmol) and5-butenylnorbornene (3.26 g, 0.022 mol). This mixture was diluted with16 ml of toluene. To this mixture was added 50 μl of a toluene solutionof (allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 1.3mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 2.85 g of polymer was obtained. Yield 57%. Mw=154,000and Mn=59,000 as determined by GPC methods. The polymer containedapproximately 25% 5-butenylnorbornene according to ¹H NMR analysis.

EXAMPLE 73

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol) and 5-butenylnorbornene (0.05 g, 0.33mmol). This mixture was diluted with 16 ml of toluene. To this mixturewas added 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 4.28 g of polymer was obtained. Yield 86%. Mw=1,886,000and Mn=328,000 as determined by GPC methods.

EXAMPLE 74

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol) and 5-butenylnorbornene (0.15 g, 1.0mmol). This mixture was diluted with 16 ml of toluene. To this mixturewas added 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 4.00 g of polymer was obtained. Yield 80%. Mw=957,000and Mn=267,000 as determined by GPC methods.

EXAMPLE 75

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol) and 5-butenylnorbornene (0.25 g, 1.7mmol). This mixture was diluted with 16 ml of toluene. To this mixturewas added 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 4.32 g of polymer was obtained. Yield 86%. Mw=460,000and Mn=119,000 as determined by GPC methods.

EXAMPLE 76

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol), and hexene-1 (0.31 g, 3.6 mmol).This mixture was diluted with 16 ml of toluene. To this mixture wasadded 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 3.13 g of polymer was obtained. Yield 63%. Mw=2,050,000and Mn=682,000 as determined by GPC methods.

EXAMPLE 77

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol), and hexene-1 (0.69 g, 8.2 mmol).This mixture was diluted with 16 ml of toluene. To this mixture wasadded 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 2.01 g of polymer was obtained. Yield 40%. Mw=1,275,000and Mn=548,000 as determined by GPC methods.

EXAMPLE 78

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol), and hexene-1 (1.83 g, 22.0 mmol).This mixture was diluted with 16 ml of toluene. To this mixture wasadded 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 1.28 g of polymer was obtained. Yield 26%. Mw=532,000and Mn=190,000 as determined by GPC methods.

EXAMPLE 79

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol), and 5-vinylnorbornene (0.21 g, 1.7mmol). This mixture was diluted with 16 ml of toluene. To this mixturewas added 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 1.28 g of polymer was obtained. Yield 14%.

EXAMPLE 80

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol), and 5-ethylidenenorbornene (0.21 g,1.7 mmol). This mixture was diluted with 16 ml of toluene. To thismixture was added 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 1.7 g of polymer was obtained. Yield 34%.

EXAMPLE 81

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (100 μl of a 0.0016 Msolution in toluene, 0.00016 mmol), and 5-ethylidenenorbornene (0.43 g,3.6 mmol). This mixture was diluted with 16 ml of toluene. To thismixture was added 50 μl of a toluene solution of(allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B, 0.65mMol). The mixture was heated to 65° C. for 18 hours. The viscoussolution was diluted with toluene and then the polymer was precipitatedinto an excess of acetone. After filtering and drying in vacuo overnighta conversion of 1.4 g of polymer was obtained. Yield 28%.

EXAMPLE 82

To a mixture of butylnorbornene (4.58 g, 30.5 mmol) and5-triethoxysilylnorbornene (0.420 g, 1.64 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.0010 g, 0.0012 mmol). Thismixture was diluted with 16 ml of toluene. To this mixture was added(allyl)platinum chloride tetramer (Catalyst P, 100 μl of a 0.054 mMolsolution in toluene) and tricyclohexylphosphine (100 μl of a 0.11 mMolsolution in toluene). The mixture was heated to 65° C. for 64 hours. Thepoured into an excess of acetone. After filtering and drying in vacuoovernight a conversion of 0.11 g of polymer was obtained. Yield 2%.

EXAMPLE 83

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted with 18 ml of toluene. A mixture of (allyl)palladiumchloride dimer (0.000062 mmol) and triphenylphosphine (0.00013 mmol) intoluene and added to the monomer solution. The mixture was heated to 65°C. for 4 hours. The resulting mixture was poured into acetone toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 2.6 g (26%).

EXAMPLE 84

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0013 mmol). Thismixture was diluted to a total volume 18 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00013 mmol) and triphenylphosphine(0.00025 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 8.8 g (88%).

EXAMPLE 85

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 18 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.000031 mmol) and triphenylphosphine(0.000063 mmol) in toluene and added to the monomer solution. Themixture was heated to 65° C. for 4 hours. The resulting mixture waspoured into acetone to precipitate the polymer which was filtered anddried in vacuo overnight. Yield 2.3 g (23%).

EXAMPLE 86

To a mixture of butylnorbornene (4.2 g, 28.1 mmol) and5-triethoxysilylnorbornene (0.8 g, 3.1 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 100 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.000062 mmol) and triphenylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 1.2 g (24%).

EXAMPLE 87

To a mixture of butylnorbornene (4.2 g, 28.1 mmol) and5-triethoxysilylnorbornene (0.8 g, 3.1 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O) (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 64 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.000062 mmol) and triphenylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 1.3 g (26%).

EXAMPLE 88

To a mixture of butylnorbornene (4.2 g, 28.1 mmol) and5-triethoxysilylnorbornene (0.8 g, 3.1 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 100 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.000062 mmol) and triphenylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 3.0 g (60%).

EXAMPLE 89

To a mixture of butylnorbornene (4.2 g, 28.1 mmol) and5-triethoxysilylnorbornene (0.8 g, 3.1 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.000062 mmol) and triphenylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 4.5 g (90%).

EXAMPLE 90

To a mixture of butylnorbornene (4.2 g, 28.1 mmol) and5-triethoxysilylnorbornene (0.8 g, 3.1 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 100 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.000062 mmol) and triphenylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 18 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 10.5 g (21%).

EXAMPLE 91

To a mixture of butylnorbornene (4.2 g, 28.1 mmol) and5-triethoxysilylnorbornene (0.8 g, 3.1 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 64 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.000062 mmol) and triphenylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 1.25 g (25%).

EXAMPLE 92

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. About 28 μl ofcyclopentene (0.32 mmol) was added. A mixture of (allyl)palladiumchloride dimer (0.000062 mmol) and triphenylphosphine (0.00013 mmol) intoluene and added to the monomer solution. The mixture was heated to 65°C. for 4 hours. The resulting mixture was poured into acetone toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 1.4 g (28%). Mw=2,530,000 and Mn=1,340,000 as determined by GPCmethods.

EXAMPLE 93

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. About 144 μlof cyclopentene (1.64 mmol) was added. A mixture of (allyl)palladiumchloride dimer (0.000062 mmol) and triphenylphosphine (0.00013 mmol) intoluene and added to the monomer solution. The mixture was heated to 65°C. for 4 hours. The resulting mixture was poured into acetone toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 0.7 g (14%). Mw=1,230,000 and Mn=582,000 as determined by GPCmethods.

EXAMPLE 94

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. About 305 μlof cyclopentene (3.46 mmol) was added. A mixture of (allyl)palladiumchloride dimer (0.000062 mmol) and triphenylphosphine (0.00013 mmol) intoluene and added to the monomer solution. The mixture was heated to 65°C. for 4 hours. The resulting mixture was poured into acetone toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 0.6 g (12%). Mw=802,000 and Mn=311,000 as determined by GPCmethods.

EXAMPLE 95

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.000062 mmol) and triphenylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 100° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 4.1 g (82%).

EXAMPLE 96

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.3 mg, 0.0003 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00016 mmol) and tributylphosphine(0.00032 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 0.9 g (18%). Mw=1,920,000 and Mn=845,000 as determinedby GPC methods.

EXAMPLE 97

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00006 mmol) and tributylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 1.65 g (33%).

EXAMPLE 98

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00016 mmol) and triphenylphosphine(0.00032 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 3.55 g (71%).

EXAMPLE 99

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.3 mg, 0.0003 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00016 mmol) and tri-o-tolylphosphine(0.00032 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 0.25 g (5%).

EXAMPLE 100

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00016 mmol) and tri-o-tolylphosphine(0.00032 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 0.75 g (15%). Mw 301,000 and Mn=133,000 as determinedby GPC methods.

EXAMPLE 101

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.3 mg, 0.0003 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00016 mmol) andtricyclohexylphosphine (0.00032 mmol) in toluene and added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting mixture was poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 0.3 g (6%).Mw=1,630,000 and Mn=816,000 as determined by GPC methods.

EXAMPLE 102

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00006 mmol) andtricyclohexylphosphine (0.00013 mmol) in toluene and added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting mixture was poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 4.9 g (98%).

EXAMPLE 103

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.3 mg, 0.0003 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00016 mmol) and tri-i-propylphosphine(0.00032 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 0.8 g (16%). Mw=1,770,000 and Mn=862,000 as determinedby GPC methods.

EXAMPLE 104

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00006 mmol) and tri-i-propylphosphine(0.00013 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 1.7 g (34%).

EXAMPLE 105

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium chloride dimer (0.00016 mmol) and tri-i-propylphosphine(0.00032 mmol) in toluene and added to the monomer solution. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was poured intoacetone to precipitate the polymer which was filtered and dried in vacuoovernight. Yield 3.7 g (74%).

EXAMPLE 106

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(β-pinenyl)palladium chloride dimer (Catalyst J, 0.00006 mmol) andtricyclohexylphosphine (0.00013 mmol) in toluene and added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting mixture was poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 1.65 g (35%).

EXAMPLE 107

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(β-pinenyl)palladium chloride dimer (Catalyst J, 0.00016 mmol) andtricyclohexylphosphine (0.00032 mmol) in toluene and added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting mixture was poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 4.9 g (98%).

EXAMPLE 108

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium iodide dimer (Catalyst K, 0.00006 mmol) andtricyclohexylphosphine (0.00013 mmol) in toluene and added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting mixture was poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 0.25 g (5%).

EXAMPLE 109

To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol). Thismixture was diluted to a total volume 16 ml with toluene. A mixture of(allyl)palladium iodide dimer (Catalyst K, 0.00016 mmol) andtricyclohexylphosphine (0.00032 mmol) in toluene and added to themonomer solution. The mixture was heated to 65° C. for 4 hours. Theresulting mixture was poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 0.75 g (15%).

EXAMPLE 110

A mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol), and dimethylaniliniumtetrakis(pentafluorophenylborate) (0.0013 g, 0.0016 mmol) was prepared.This mixture was diluted to a total volume 10 ml with toluene. About0.05 ml of a 0.00623 M toluene solution of(allyl)palladium(tricyclohexylphosphine)(methyl) was added. The mixturewas heated to 65° C. for 4 hours. The resulting mixture was diluted withtoluene and poured into acetone to precipitate the polymer which wasfiltered and dried in vacuo overnight. Yield 3.6 g (72%).

EXAMPLE 111

The experiment above was repeated using dimethylaniliniumtetrakis(bis(3,5-trifluoromethyl)phenyl)borate instead of thetetrakis(pentafluorophenyl)borate salt. Yield 5.0 g (100%).

EXAMPLE 112

The experiment above was repeated using trityltetrakis(pentafluorophenyl)borate instead of dimethylaniliniumtetrakis(bis(3,5-trifluoromethyl)phenyl)borate. Yield 2.8 g (56%).

EXAMPLE 113

A mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was prepared. This mixturewas diluted to a total volume 10 ml with toluene. About 0.10 ml of a3.11 mMol toluene solution of[(allyl)palladium(tricyclohexylphosphine)(ether)][tetrakis(bis(3,5-trifluoromethyl)phenyl)borate](Catalyst L) was added. The mixture was heated to 65° C. for 4 hours.The resulting mixture was poured into acetone to precipitate the polymerwhich was filtered and dried in vacuo overnight. Yield 1.4 g (28%).

EXAMPLE 114

A. To a mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.5 mg, 0.0006 mmol). Thismixture was diluted to a total volume 16 ml with toluene.(Allyl)palladium(tricyclohexylphosphine) chloride (Catalyst A, 0.00013mmol) was added to the monomer solution. The mixture was heated to 65°C. for 4 hours. The resulting mixture was poured into acetone toprecipitate the polymer which was filtered and dried in vacuo overnight.Yield 0.54 g (11%).

B. (Comparative) The experiment above was repeated, except no lithiumtetrakis(pentafluorophenyl)borate bis(diethyletherate) was added. Nopolymer was observed upon addition of the toluene reaction mixture toacetone.

C. (Comparative) The first experiment was repeated, except that(allyl)palladium chloride dimer (0.00007 mmol) was used instead of(allyl)palladium(tricyclohexylphosphine) chloride. No polymer wasobserved upon addition of the toluene reaction mixture to acetone.

EXAMPLE 115

To a 2.0 M solution of ethylnorbornene (2.0 g, 16 mmol) in toluene wasadded 0.20 ml of a 0.0016 m solution of lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O in toluene followed by 0.010ml of a 0.0062 M solution of (allyl)palladium(tricyclohexylphosphine)triflate (Catalyst B). The solution was heated to 75° C. for 1 hour. Theresulting viscous solution was diluted with toluene and poured into anexcess of acetone to precipitate the polymer. Yield 1.5 g (74%).

EXAMPLE 116

A 1.3 M solution of norbornene (2.0 g, 21 mmol) in toluene was prepared.In a separate vial added about 100 μl of a 0.0088 M solution of lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O in toluene and about 100 μlof a 0.0018 M solution of(methallyl)nickel(tricyclohexylphosphine)(triflate) (Catalyst Q) intoluene were mixed. This mixture was added to the norbornene solutionand heated to 65° C. for 18 hours. The resulting viscous solution wasdiluted with toluene and poured into an excess of methanol toprecipitate the polymer. Yield 1.8 g (92%).

EXAMPLE 117

A solution of butylnorbornene (4.6 g, 31 mmol) and the ethylester of5-carboxylic acid of norbornene (0.27 g, 1.6 mmol) in toluene (16 mltotal) was prepared. In a separate vial added about 100 μl of a 0.0088 Msolution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O intoluene and about 100 μl of a 0.0022 M solution of(allyl)palladium(tricyclohexylphoshine)(triflate) (Catalyst B) intoluene were mixed. This mixture was added to the monomer solution andheated to 65° C. for 18 hours. The resulting polymer puck was stirred inmethanol, filtered, and dried. Yield 3.76 g (78%).

EXAMPLE 118

A mixture of butylnorbornene (5.0 g, 33 mmol) in 25 ml of oxygenated,deionized water was prepared. In a separate vial added about 150 μl of a0.0088 m solution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂Oin toluene and about 125 μl of a 0.0022 M solution of(allyl)palladium(tricyclohexylphosphine)(triflate) (Catalyst B) intoluene were mixed. This mixture was added to the monomer mixture andheated to 65° C. for 18 hours. A lumpy, solid polymer puck, indicatinghigh conversion, separated from the water.

EXAMPLE 119

A mixture of butylnorbornene (4.6 g, 30.7 mmol) and5-triethoxysilylnorbornene (0.4 g, 1.5 mmol) was prepared. This mixturewas diluted to a total volume 16 ml with toluene. Catalyst U (0.0002 g)was dissolved in toluene and added to the monomer mixture. The solutionwas heated to 65° C. for 64 hours. The mixture formed a puck indicatinghigh conversion.

EXAMPLE 120

Butylnorbornene (4.58 g, 30.5 mmol) and 5-triethoxysilylnorbornene (0.34g, 1.3 mmol) were diluted with toluene to 16 ml total solution. Lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol),(allyl)palladium(trifluoroacetate) dimer (2.8 mg, 0.00014 mmol), andtriphenylamine (2.7 mg, 0.00027 mmol) were premixed in 3 ml toluene andthen added to the monomer mixture. The mixture was heated to 65° C. for64 hours. Polymer was precipitated by adding the reaction mixture toacetone. Yield 0.68 g (14%).

EXAMPLE 121

Butylnorbornene (4.58 g, 30.5 mmol) and 5-triethoxysilylnorbornene (0.34g, 1.3 mmol) were diluted with toluene to 16 ml total solution. Lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol),(allyl)palladium(trifluoroacetate) dimer (2.8 mg, 0.00014 mmol), andtriphenylstibine (3.8 mg, 0.00027 mmol) were premixed in 3 ml tolueneand then added to the monomer mixture. The mixture was heated to 65° C.for 64 hours. Polymer was precipitated by adding the reaction mixture toacetone. Yield 0.57 g (11%).

EXAMPLE 122

Butylnorbornene (4.58 g, 30.5 mmol) and 5-triethoxysilylnorbornene (0.34g, 1.3 mmol) were diluted with toluene to 16 ml total solution.(1,5-cyclooctadiene)palladium(methyl)chloride (100 μl of a 0.0027 Msolution in toluene, 0.00027 mmol) and tricyclohexylphosphine (100 μl ofa 0.0027 M solution in toluene, 0.00027 mmol) were mixed together. Thissolution was added to lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O(1.2 mg, 0.0014 mmol). This mixture was then added to the monomers andthe mixture was heated to 65° C. Within 1-2 hours, a puck formedindicating high conversion.

EXAMPLE 123

Hexylnorbornene (5.44 g, 30.5 mmol) and 5-triethoxysilylnorbornene (0.41g, 1.6 mmol) were diluted with toluene to 16 ml total solution alongwith lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016mmol). (Allyl)palladium(tricyclohexylphosphine)(triflate) (50 μl of a0.0062 M solution in toluene, 0.00032 mmol) was added. This mixture wasthen added to the monomers and the mixture was heated to 65° C. Within 3hours, the mixture become highly viscous. After 18 hours, the polymerwas precipitated, filtered, and dried. Yield 5.54 g (95%).

EXAMPLE 124

Hexylnorbornene (5.16 g, 29.0 mmol), 5-triethoxysilylnorbornene (0.82 g,3.2 mmol), and hexene-1 (0.26 g, 3.1 mmol) were diluted with toluene to19 ml total volume along with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol). Thecontents were warmed to 65° C. and(allyl)palladium(tricyclohexylphosphine)(triflate) (0.00032 mmol) wasadded in toluene. After 18 hours, the viscous mixture was diluted withadditional toluene and added to acetone. The precipitated polymer wasfiltered and dried. Yield 6.0 g (100%). Mw=1,079,000 and Mn=320,000 asdetermined by GPC methods.

EXAMPLE 125

Hexylnorbornene (5.16 g, 29.0 mmol), 5-triethoxysilylnorbornene (0.82 g,3.2 mmol), and hexene-1 (0.52 g, 6.2 mmol) were diluted with toluene to19 ml total volume along with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol). Thecontents were warmed to 65° C. and(allyl)palladium(tricyclohexylphosphine)(triflate) (0.00032 mmol) wasadded in toluene. After 18 hours, the viscous mixture was diluted withadditional toluene and added to acetone. The precipitated polymer wasfiltered and dried. Yield 6.0 g (100%). Mw=762,000 and Mn=166,000 asdetermined by GPC methods.

EXAMPLE 126

Hexylnorbornene (3.73 g, 21.0 mmol), 5-triethoxysilylnorbornene (0.82 g,3.2 mmol), cyclohexenylnorbornene (1.40 g, 8.1 mmol) and hexene-1 (0.13g, 1.6 mmol) were diluted with toluene to 19 ml total volume along withlithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016mmol). The contents were warmed to 65° C. and(allyl)palladium(tricyclohexylphosphine)(triflate) (0.00032 mmol) wasadded in toluene. After 18 hours, the viscous mixture was diluted withadditional toluene and added to acetone. The precipitated polymer wasfiltered and dried. Yield 0.97 g (16%).

EXAMPLE 127

Hexylnorbornene (3.73 g, 21.0 mmol), 5-triethoxysilylnorbornene (0.82 g,3.2 mmol), cyclohexenylnorbornene (1.40 g, 8.1 mmol) and hexene-1 (0.26g, 3.2 mmol) were diluted with toluene to 19 ml total volume along withlithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016mmol). The contents were warmed to 65° C. and(allyl)palladium(tricyclohexylphosphine)(triflate) (0.00032 mmol) wasadded in toluene. After 18 hours, the viscous mixture was diluted withadditional toluene and added to acetone. The precipitated polymer wasfiltered and dried. Yield 0.89 g (15%). Mw=115,000 and Mn=50,000 asdetermined by GPC methods.

EXAMPLE 128

Hexylnorbornene (3.73 g, 21.0 mmol), 5-triethoxysilylnorbornene (0.82 g,3.2 mmol), cyclohexenylnorbornene (1.40 g, 8.1 mmol) and hexene-1 (0.52g, 6.4 mmol) were diluted with toluene to 19 ml total volume along withlithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016mmol). The contents were warmed to 65° C. and(allyl)palladium(tricyclohexylphosphine)(triflate) (0.00032 mmol) wasadded in toluene. After 18 hours, the viscous mixture was diluted withadditional toluene and added to acetone. The precipitated polymer wasfiltered and dried. Yield 0.89 g (15%). Mw=100,000 and Mn=40,000 asdetermined by GPC methods.

EXAMPLE 129

Hexylnorbornene (5.16 g, 29.0 mmol), 5-triethoxysilylnorbornene (0.82 g,3.2 mmol), and hexene-1 (0.26 g, 3.2 mmol) were diluted with cyclohexaneto 30 ml total volume along with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol). Thecontents were warmed to 65° C. and(allyl)palladium(tricyclohexylphosphine) (trifluoroacetate) (0.00027mmol) was added in toluene. After 18 hours the polymer was precipitatedinto acetone, filtered and dried. Yield 3.6 g (60%).

EXAMPLE 130

Butylnorbornene (1.57 g, 10.5 mmol), 5-triethoxysilylnorbornene (0.41 g,1.6 mmol), and dicyclopentadiene (0.53 g, 4.0 mmol) were diluted withtoluene to 30 ml total volume along with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.7 mg, 0.0008 mmol). Thecontents were warmed to 65° C. and(allyl)palladium(tricyclohexylphosphine) (trifluoroacetate) (0.00016mmol) was added in toluene. After 18 hours the mixture had gelledindicating high conversion.

EXAMPLE 131

Butylnorbornene (5.0 g, 33 mmol) was added to a deareated water (50 ml)solution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (14.5 mg,0.016 mmol). The mixture was placed into a blender under nitrogen. Thecatalyst, (allyl)palladium dimer (0.61 mg, 0.0017 mmol), and ligand,tricyclohexylphosphine (0.93 mg, 0.0033 mmol), in 0.5 ml of toluene wasadded to the blender. The mixture was stirred at high speed at roomtemperature for 6 min. The polymer formed was isolated by filtration anddried. Yield 0.9 g (18%).

EXAMPLE 132

Butylnorbornene (10.0 g, 66.7 mmol) and 0.17 ml of a 30% aqueoussolution of sodium lauryl sulfate was added to a deareated water (100ml) solution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (29mg, 0.033 mmol). The mixture was stirred rapidly with a mechanicalstirrer for 5 minutes. The catalyst, (allyl)palladium dimer (1.22 mg,0.00332 mmol), and ligand, tricyclohexylphosphine (1.86 mg, 0.00667mmol), in 1.0 ml of toluene was added to the mixture. The mixture wasstirred at room temperature for about 4 hours. A large portion ofpolymer with large particle size and a milky solution resulted. Thelarge portion of polymer was dissolved in toluene, precipitated inacetone, filtered and dried to give 6.8 g (68%) of polymer. The milkysolution, essentially an emulsion, was added to acetone (100 ml) to give0.7 g (7%) of white powder after filtering and drying.

EXAMPLE 133

Butylnorbornene (10.0 g, 66.7 mmol) and 0.17 ml of a 30% aqueoussolution of sodium lauryl sulfate was added to a deareated water (100ml) solution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.9mg, 0.0033 mmol). The mixture was stirred rapidly with a mechanicalstirrer for 1 hour. The catalyst, (allyl)palladium dimer (0.12 mg,0.00033 mmol), and ligand, tricyclohexylphosphine (0.19 mg, 0.00067mmol), in 0.1 ml of toluene was added to the mixture. The mixture wasstirred at room temperature for about 4 hours. A milky solutionresulted. The milky solution, essentially an emulsion, was added toacetone (100 ml) to give 0.25 g (2.5%) of white powder after filteringand drying.

EXAMPLE 134

Methylacetate of 5-norbornene methanol (5.0 g, 30 mmol) was added to adeareated water (100 ml) solution of lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (13 mg, 0.015 mmol). Themixture was stirred rapidly with a magnetic stirrer. The catalyst,(allyl)palladium dimer (0.55 mg, 0.0015 mmol), and ligand,tricyclohexylphosphine (0.84 mg, 0.0030 mmol), in 0.1 ml of toluene wasadded to the mixture. The mixture was stirred at room temperature forabout 4 hours at 65° C. A powdery polymer was subsequently precipitated.Yield 0.25 g (5%).

EXAMPLE 135

Butylnorbornene (5.0 g, 33 mmol) was added to a deareated water (100 ml)solution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.9 mg,0.0033 mmol) in the presence of 0.5 wt % sodium lauryl sulfate. Themixture was stirred rapidly with a magnetic stirrer. The catalyst,(allyl)palladium dimer (0.12 mg, 0.00033 mmol), and ligand,tricyclohexylphosphine (0.19 mg, 0.00067 mmol), in 0.1 ml of toluene wasadded to the mixture. The mixture was stirred at room temperature for 4hours. A milky solution and precipitated polymer resulted. About 2.1 g(42% yield) of polymer was isolated.

EXAMPLE 136

Butylnorbornene (5.0 g, 33 mmol) was added to a deareated water (50 ml)solution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.9 mg,0.0033 mmol) in the presence of 1.0 wt % sodium lauryl sulfate. Themixture was stirred rapidly with a magnetic stirrer. The catalyst,(allyl)palladium dimer (0.12 mg, 0.00033 mmol), and ligand,tricyclohexylphosphine (0.19 mg, 0.00067 mmol), in 0.1 ml of toluene wasadded to the mixture. The mixture was stirred at room temperature for 4hours. A milky solution and precipitated polymer resulted. About 1 g(20% yield) of polymer was isolated.

EXAMPLE 137

Butylnorbornene (5.0 g, 33 mmol) was added to a deareated water (100 ml)solution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.9 mg,0.0033 mmol) in the presence of 0.5 wt % sodium lauryl sulfate. Themixture was stirred rapidly with a mechanical stirrer. The catalyst,(allyl)palladium dimer (0.12 mg, 0.00033 mmol), and ligand,tricyclohexylphosphine (0.19 mg, 0.00067 mmol), in 0.1 ml of toluene wasadded to the mixture. The mixture was stirred at room temperature for 4hours at 65° C. A milky solution and precipitated polymer resulted.About 3.3 g (66%) of polymer was isolated after dissolving the polymerin toluene and precipitating in acetone, filtering, and drying.

EXAMPLE 138

Butylnorbornene (5.0 g, 33 mmol) was added to a deareated water (5 ml)solution of lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (5.4 mg,0.0064 mmol) in the presence of 0.5 wt % sodium lauryl sulfate. Themixture was stirred rapidly with a magnetic stirrer. The catalyst,(allyl)palladium dimer (0.24 mg, 0.00064 mmol), and ligand,tricyclohexylphosphine (0.36 mg, 0.0013 mmol), in 100 ml of toluene wasadded to the mixture. The mixture was stirred at room temperature for 4hours at 65° C. A milky solution and precipitated polymer resulted. Theparticle size of the polymer in the milky solution was determined to beabout 181 nm with a polydispersity of 2.6. The amount of polymercontained in the water emulsion constituted about 0.31 g (6.2% yield).The precipitated polymer was dried overnight and gave 2.0 g (40%) yield.

EXAMPLE 139

(Allyl)palladium chloride dimer (0.0049 g, 0.013 mmol) and the sodiumsalt tri(m-sulfonatophenyl)phosphine (0.015 g, 0.026 mmol) weredissolved in 4 ml of deareated water. Butylnorbornene (5.0 g, 33 mmol)was added to a deareated water (50 ml) solution of lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (5.4 mg, 0.0064 mmol). Themixture was stirred rapidly with a magnetic stirrer. About 100 μl of theaqueous catalyst solution was added to the monomer solution afterheating the monomer mixture to 65° C. After 1 hour, the precipitatedpolymer/water mixture was poured into methanol, filtered, and dried.Yield 4.45 g (89%).

EXAMPLE 140

To a mixture of butylnorbornene (5.0 g, 33 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene. Approximately 100 μl of a toluene stock solution of(allyl)palladium(tricyclohexylphosphine) trifluoroacetate (Catalyst C,3.0 mMol) and 100 μl of a toluene stock solution of ether-free lithiumtetrakis(pentafluorophenyl)borate (14.9 mMol) were combined together anddiluted with 2 ml of toluene, then added to the monomer mixture. Themixture was heated to 80° C. for 1 hour. A solid puck formed, indicatinghigh 5 conversion.

EXAMPLE 141

To a mixture of butylnorbornene (5.0 g, 33 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene. Approximately 100 μl of a toluene stock solution of(allyl)palladium(tricyclohexylphosphine) trifluoroacetate (Catalyst C,3.0 mMol) and 100 μL of a toluene/THF (98:2) stock solution of potassiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate (14.9 mMol) were combinedtogether and diluted with 2 ml of toluene, then added to the monomermixture. The mixture was heated to 80° C. for 1 hour. A solid puckformed, indicating high conversion.

EXAMPLE 142

To a mixture of butylnorbornene (5.0 g, 33 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene. Approximately 100 μl of a toluene stock solution of(allyl)palladium(tricyclohexylphosphine) trifluoroacetate (Catalyst C,3.0 mMol) and 100 μl of a toluene stock solution of sodiumtetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boratetrihydrate (14.9 mMol) were combined together and diluted with 2 ml oftoluene, then added to the monomer mixture. The mixture was heated to80° C. for 1 hour. A solid puck formed, indicating high conversion.

EXAMPLE 143

To a mixture of butylnorbornene (5.0 g, 33 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene. Approximately 10 μl of a toluene stock solution of(allyl)palladium(tricyclohexylphosphine) trifluoroacetate (Catalyst C, 3mMol) and 100 μl of a toluene stock solution of sodiumtetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boratetrihydrate (0.76 mMol) were combined together and diluted with 2 ml oftoluene, then added to the monomer mixture. The mixture was heated to80° C. for 18 hours. A viscous solution formed, which was diluted withtoluene and precipitated into an excess of methanol to isolate thepolymer. After filtration and drying in vacuo overnight a conversion of2.32 g of polymer was obtained. Yield 39%. Mw=2,580,000 Mn=913,000 asdetermined by GPC methods.

EXAMPLE 144

To a mixture of butylnorbornene (5.0 g, 33 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene. Approximately 100 μl of a toluene stock solution of(allyl)palladium(tricyclohexylphosphine) chloride (Catalyst A, 3.0 mMol)and 100 μL of a toluene stock solution of Ag[CB₁₁H₆Br₆] (14.9 mMol) werecombined together and diluted with 2 ml of toluene in the absence oflight. The solution was then filtered to remove AgCl and then added tothe monomer mixture. The mixture was heated to 80° C. for 18 hours. Aslightly viscous solution formed, which was diluted with toluene andprecipitated into an excess of acetone to isolate the polymer. Afterfiltration and drying in vacuo overnight, 0.34 g (6% yield) of polymerwas obtained. Mw=253,000 Mn=87,000 as determined by GPC methods.

EXAMPLE 145

To a mixture of butylnorbornene (5.00 g, 33.0 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml ofdichloromethane. Approximately 100 μl of a toluene stock solution of(allyl)palladium(tricyclohexylphosphine) trifluoroacetate (Catalyst C, 3mMol) was combined with lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (0.0015 g, 0.0017 mmol) in 0.5 ml of toluene, then added to themonomer mixture. The mixture was reacted at 25° C. for 18 hours. A solidpuck formed, indicating high conversion.

EXAMPLE 146

To a bottle containing 5-triethoxysilylnorbornene (9.47 g, 37.0 mmol)was added 12 ml of toluene. Approximately 100 μl of a toluene stocksolution of (allyl)palladium(tricyclohexylphosphine) trifluoroacetate(Catalyst C, 3 mMol) and 100 μl of a toluene stock solution ofether-free lithium tetrakis(pentafluorophenyl)borate (14.9 mMol) werecombined together and diluted with 2 ml of toluene, then added to themonomer mixture. The mixture was heated to 80° C. for 2 hours. A veryviscous solution formed, which was diluted with toluene and precipitatedinto an excess of methanol to isolate the polymer. After filtration anddrying in vacuo overnight, a conversion of 3.84 g was obtained. Yield41%. Mw=1,540,000 Mn=417,000 as determined by GPC methods.

EXAMPLE 147

To a mixture of butylnorbornene (5.00 g, 33.0 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene, all having been stored for weeks in the air. Approximately 100μl of a toluene stock solution of(allyl)palladium(tricyclohexylphosphine) trifluoroacetate (Catalyst C, 3mMol) and 100 μl of a toluene stock solution of lithiumtetrakis(pentafluorophenyl)borate (14.9 mMol) were combined together anddiluted with 2 ml of toluene, then added to the monomer mixture. Themixture was heated to 80° C. for 18 hours. A slightly viscous solutionresulted, which was diluted with toluene and precipitated into an excessof acetone to isolate the polymer. After filtration and drying in vacuoovernight, a conversion of 0.35 g was obtained. Yield 6%. Mw=772,000Mn=420,000 as determined by GPC.

EXAMPLE 148

To a mixture of butylnorbornene (5.00 g, 33.0 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene. Approximately 50 μl of a toluene stock solution of(allyl)palladiumchloride dimer (3.0 mMol) and 50 μl of a toluene stocksolution of tris(trimethylsilyl)phosphite (6.0 mMol) were combinedtogether and diluted with 2 ml of toluene, then added to a solution ofether-free lithium tetrakis(pentafluorophenyl)borate (0.0010 g, 0.0014mmol) in 1 ml of toluene. The catalyst solution was then added to themonomer solution, and the mixture was heated to 80° C. for 18 hours. Aviscous solution formed which was diluted with toluene and precipitatedinto an excess of acetone to isolate the polymer. After filtration anddrying in vacuo overnight, a conversion of 2.35 g was obtained. Yield39%.

EXAMPLE 149

To a mixture of butylnorbornene (5.00 g, 33.0 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene. Approximately 50 μl of a toluene stock solution of(allyl)palladiumchloride dimer (3.0 mMol) and 50 μl of a toluene stocksolution of tris(trimethylsilyl)phosphine (6.0 mMol) were combinedtogether and diluted with 2 ml of toluene, then added to a solution ofether-free lithium tetrakis(pentafluorophenyl)borate (0.0010 g, 0.0014mmol) in 1 ml of toluene. The catalyst solution was then added to themonomer solution, and the mixture was heated to 80° C. for 18 hours. Aviscous solution formed which was diluted with toluene and precipitatedinto an excess of acetone to isolate the polymer. After filtration anddrying in vacuo overnight, a conversion of 2.60 g was obtained. Yield44%.

EXAMPLE 150

To a mixture of butylnorbornene (5.00 g, 33 mmol) and5-triethoxysilylnorbornene (0.95 g, 3.7 mmol) was added 12 ml oftoluene. Approximately 50 μl of a toluene stock solution of(allyl)palladiumchloride dimer (3.0 mMol) and 50 μl of a toluene stocksolution of tri-o-xenylphosphite (6.0 mMol) were combined together anddiluted with 2 ml of toluene, then added to a solution of ether-freelithium tetrakis(pentafluorophenyl)borate (0.0010 g, 0.0014 mmol) in 1ml of toluene. The catalyst solution was then added to the monomersolution, and the mixture was heated to 80° C. for 18 hours. A slightlyviscous solution formed which was diluted with toluene and precipitatedinto an excess of acetone to isolate the polymer. After filtration anddrying in vacuo overnight, a conversion of 1.86 g was obtained. Yield31%. Mw=96,000 Mn=31,000 as determined by GPC methods.

EXAMPLE 151

Butylnorbornene (5 g, 0.033 mol) and triethoxysilylnorbornene (0.95 g,0.0037 mol) were dissolved in toluene (2 M solution of monomers).(Allyl)palladium(tricyclohexylphosphine)chloride (0.00031 mmol) andAgBF₄ (0.00031 mmol) were combined in toluene. The mixture was thenadded to the monomers. This mixture was heated to 80° C. for 18 hours.The mixture was then added to methanol. No polymer precipitated.

EXAMPLE 152

Butylnorbornene (5.0 g, 0.033 mol), triethoxysilylnorbornene (0.95 g,0.0037 mol), and lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O(0.0013 g, 0.0015 mmol) were dissolved in toluene (2 M solution ofmonomers). (Allyl)palladium(tricyclohexylphosphine)chloride (0.00031mmol) and AgBF₄ (0.00031 mmol) were combined in toluene. This solutionwas added to the monomers. This mixture was heated to 80° C. for 1 hour.A puck formed indicating high conversion.

EXAMPLE 153

Butylnorbornene (5.0 g, 0.033 mol) and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.0013 g, 0.0015 mmol) weredissolved in toluene (2 M solution of monomers). About 100 μl of an(allyl)palladiumchloride dimer (1.4 mmol) solution in toluene was addedto a 100 μl solution of1,3,5,7,9,11,13-heptacyclopentyl-15-[2-(diphenylphosphino)ethyl]pentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane(2.8 mmol) solution in toluene. This mixture was added to the monomermixture. After 5 minutes at room temperature a polymeric puck formedindicating high conversion.

EXAMPLE 154

Butylnorbornene (5.0 g, 0.033 mol) and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.0013 g, 0.0015 mmol) weredissolved in toluene (2 M solution of monomers). About 100 μl of an(allyl)palladiumchloride dimer (1.4 mmol) solution in toluene was addedto a 100 μl solution of Sb(SPh)₃ (2.8 mmol) solution in toluene. Thismixture was added to the monomer mixture. After 64 hours at 80° C. themixture was poured into acetone to precipitate the polymer, which wasfiltered and dried. Yield 3.4 g (68%).

EXAMPLE 155

Butylnorbornene (5.0 g, 0.033 mol) and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.0013 g, 0.0015 mmol) weredissolved in toluene (2 M solution of monomers). About 100 μl of an(allyl)palladiumchloride dimer (1.4 mmol) solution in toluene was addedto a 100 μl solution of tris(2,4-di-t-butyl)phenylphosphite (2.8 mmol)solution in toluene. This mixture was added to the monomer mixture.After 1 minute at room temperature a polymeric puck formed indicatinghigh conversion.

EXAMPLE 156

Butylnorbornene (5.0 g, 0.033 mol) and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.0013 g, 0.0015 mmol) weredissolved in toluene (2 M solution of monomers). About 100 μl of an(allyl)palladiumchloride dimer (1.4 mmol) solution in toluene was addedto a 100 μl solution ofbis(trimethylsilyl)aminobis(trimethylsilylimino)phosphine (2.8 mmol)solution in toluene. This mixture was added to the monomer mixture.After heating the mixture to 80° C. for 2 hours the solution was addedto acetone to precipitate the polymer. The polymer was filtered anddried. Yield 2.4 g (48%).

EXAMPLE 157

A 50 weight percent solution of butylnorbornene (5.0 g, 0.033 mol) wasprepared in toluene. Lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O(0.0012 g, 0.0014 mmol) was combined with (allyl)palladiumchloride dimer(100 μl of a 1.4 mmol solution in toluene) and triphenylamine (100 μl ofa 2.7 mmol solution in toluene) in toluene and added to the monomermixture. A polymeric puck formed within 5-10 min at room temperature.

EXAMPLE 158

A 50 weight percent solution of butylnorbornene (5.0 g, 0.033 mol) wasprepared in toluene. Lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O(0.0012 g, 0.0014 mmol) was combined with(allyl)platinum(tricyclohexylphosphine)triflate (100 μl of a 2.8 mmolsolution in toluene) in toluene and added to the monomer mixture. Themixture was heated to 80° C. for 18 hours. The mixture was poured intoacetone to precipitate the polymer. After filtering and drying, 0.15 gof polymer was isolated (3% yield).

EXAMPLE 159

To a thick-walled, septum-sealed glass vial, equipped with a magneticstir-bar was added 5-butylnorbornene (7.95 g, 53 mmol), toluene (19 ml),palladium ethylhexanoate (82 μl, 0.35 μmol), tricyclohexylphosphine (28μl, 0.35 μmol), tris(pentafluorophenyl)boron (126 μl, 6.36 μmol) andtriethylaluminum (4.2 μl, 1.7 molar in cyclohexane), 7.0 μmol). (Ratioof monomer to palladium, 150,000:1) The resulting stirred solution wasplaced in a heated oil bath at 67° C. for a total of 3 hours. Withinless than 30 minutes the colorless, clear solution was a highly viscousmass that could no longer be stirred. After 3 hours the colorless gelwas isolated by breaking the flask, was cut into small pieces using ablade and the material was dissolved in boiling toluene (800 ml) over aperiod of several hours. The polymer was precipitated by pouring intoexcess methanol (1 liter), filtered and washed with excess methanolprior to drying to constant weight under vacuum at 80° C.

The dried, white, granular polymer was found to weigh 7.76 g (97.6%conversion). Proton NMR revealed the polymer to be free of any solventsor unconverted monomer.

EXAMPLE 160

To a thick-walled, septum-sealed glass vial, equipped with a magneticstir bar was added 5-butylnorbornene (7.57 g, 50.4 mmol),triethoxysilylnorbornene (0.68 g, 2.6 mmol), toluene (20 ml), palladiumethylhexanoate (82 μl, 0.35 mol), tricyclohexylphosphine (28 μl, 0.35mol), tris(pentafluorophenyl)boron (126 μl, 6.36 mol) andtriethylaluminum (4.2 μl (1.7 molar in cyclohexane), 7.0 mol). (Ratio ofmonomers to palladium, 150,000:1). The resulting stirred solution wasplaced in a heated oil bath at 67° C. for a total of 4 hours. Within 60minutes the colorless, clear solution was a highly viscous mass thatcould no longer be stirred. After 4 hours the colorless gel was isolatedby breaking the flask, was cut into small pieces using a blade and thematerial was dissolved in hot toluene. The polymer was precipitated bypouring into excess acetone, filtered and washed with excess acetoneprior to drying to constant weight under vacuum at 80° C. The dried,white, granular polymer was found to weigh 4.5 g (55% conversion).Proton NMR revealed the polymer to be a copolymer of butylnorbornene andtriethoxysilylnorbornene.

EXAMPLE 161

To a thick-walled, septum-sealed glass vial, equipped with a magneticstir bar was added 5-butylnorbornene (7.57 g, 50.4 mmol),triethoxysilylnorbornene (0.68 g, 2.6 mmol), toluene (10 ml), palladiumethylhexanoate (0.52 μmol), tricyclohexylphosphine (0.52 μmol),tris(pentafluorophenyl)boron (4.6 μmol) and triethylaluminum (5.2 μmol).(Ratio of monomers to palladium 100,000: 1.) The resulting stirredsolution was placed in a heated oil bath at 65° C. for a total of 3hours. Within 90 minutes the colorless, clear solution was a highlyviscous mass that could no longer be stirred. After 3 hours thecolorless gel was isolated by breaking the flask, was cut into smallpieces using a blade and the material was dissolved in hot toluene. Thepolymer was precipitated by pouring into excess acetone, filtered andwashed with excess acetone prior to drying to constant weight undervacuum at 80° C. The dried, white, granular polymer was found to weigh5.7 g (70% conversion).

EXAMPLE 162

To a thick-walled, septum-sealed glass vial, equipped with a magneticstir bar was added 5-butylnorbornene (7.57 g, 50.4 mmol),triethoxysilylnorbornene (0.68 g, 2.6 mmol), toluene (8 ml), palladiumethylhexanoate (2.6 μmol), tricyclohexylphosphine (2.6 μmol),tris(pentafluorophenyl)boron (23.4 μmol) and triethylaluminum (26 μmol).(Ratio of monomers to palladium, 20,000:1.) The resulting stirredsolution was placed in a heated oil bath at 65° C. Within 30 seconds thereaction exothermed violently resulting in a solid mass that no longerstirred within 45 seconds indicating that very high conversion had beenachieved despite the reaction time of less than 1 minute.

EXAMPLE 163

To a thick-walled, septum-sealed glass vial, equipped with a magneticstir bar was added 5-butylnorbornene (7.57 g, 50.4 mmol),triethoxysilylnorbornene (0.68 g, 2.6 mmol), toluene (6 ml),bis(triphenylphosphine)palladium dichloride (0.9 mg, 2.6 μmol) intoluene (3 ml), tris(pentafluorophenyl)boron (0.46 ml, 23.4 μmol) andtriethylaluminum (16 μl (1.7 molar in cyclohexane), 26 μmol). (Ratio ofmonomers to palladium, 20,000:1) The resulting stirred solution wasplaced in a heated oil bath at 65° C. for a total of 3 hours. Within 60minutes the colorless, clear solution was a highly viscous mass thatcould no longer be stirred. After 3 hours the colorless gel was isolatedby breaking the flask, was cut into small pieces using a blade and thematerial was dissolved in hot toluene. The polymer was precipitated bypouring into excess acetone, filtered and washed with excess acetoneprior to drying to constant weight under vacuum at 80° C. The dried,white, granular polymer was found to weigh 4.83 g (60% conversion).Proton NMR revealed the polymer to be a copolymer of butylnorbornene andtriethoxysilylnorbornene. The molecular weight (Mw) of the resultingcopolymer was found to be 845,000.

Comparative Example 164

To a thick-walled, septum-sealed glass vial, equipped with a magneticstir bar was added 5-butylnorbornene (7.57 g, 50.4 mmol),triethoxysilylnorbornene (0.68 g, 2.6 mmol), toluene (8 ml), palladiumethylhexanoate (2.6 μmol), tris(pentafluorophenyl)boron (23.4 μmol) andtriethylaluminum (26 μmol). (Ratio of monomers to palladium, 20,000:1).The resulting stirred solution was placed in heated oil bath at 65° C.for a total of 3 hours. The resulting polymer was precipitated bypouring into excess acetone, filtered and washed with excess acetoneprior to drying to constant weight under vacuum at 80° C. The dried,white polymer was found to weigh less than 0.1 g (less than 1.5%conversion). This shows the dramatic improvement of added phosphineligands on catalyst performance.

EXAMPLE 165

To a thick-walled, septum-sealed glass vial, equipped with a magneticstir bar was added 5-butylnorbornene (7.95 g, 53 mmol), palladiumethylhexanoate (82 μl, 0.35 μmol), tricyclohexylphosphine (28 μl, 0.35μmol), tris(pentafluorophenyl)boron (126 μl, 6.36 μmol) andtriethylaluminum (4.2 μl (1.7 molar in cyclohexane), 7.0 μmol). (Ratioof monomer to palladium, 150,000:1). There was a rapid increase inviscosity. After 10 minutes the vial was placed in a heated oil bath at70° C. for 30 minutes, then the temperature was ramped to 100° C. for afurther 30 minutes, before being heated to 130° C. for a final period of60 minutes. The colorless, transparent solid puck was allowed to cooland was then isolated by breaking the vial. The conversion of the puckwas measured using TGA methods (DuPont analyzer heated at 10° C. perminute, under nitrogen, from 30° C. to 450° C. and measuring the weightloss at 350° C.). The conversion was found to be 92%.

EXAMPLE 166

A 50 weight percent solution of butylnorbornene (5.0 g, 0.033 mol) wasprepared in toluene. Lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O(0.0012 g, 0.0014 mmol) was combined with (allyl)palladiumchloride dimer(100 μl of a 1.4 mmol solution in toluene) and 2,6-di-t-butylpyridine(100 μl of a 2.9 mmol solution in toluene) in toluene and added to themonomer mixture. A polymeric puck formed within 5-10 min at roomtemperature.

EXAMPLE 167

To a solution of LiFABA (2.0 mg) and hexylnorbornene (20 g) in 30 ml oftoluene was added bis(tricyclohexylphosphine)(hydrido)palladium(II)nitrate (0.8 mg) in 0.5 ml toluene. Ratio ofmonomer:procatalyst:activator was 100,000:1:2. The reaction was stirredfor 3.5 hours at 55° C. during which time the reaction became a rubberysolid. The solid was dissolved in toluene. The product was precipitatedin acetone and dried under vacuum to give 19.5 g, 97.5%) of whitepolymer. Mn (Daltons): 698,861, Mw (Daltons): 3,482,375, Polydispersity:4.98.

EXAMPLE 168

To a solution of LiFABA (1.9 mg) and hexylnorbornene (18.5 g) andtriethoxysilylnorbornene (1.5 g) in 30 ml of toluene was addedbis(tricyclohexylphosphine)(hydrido)palladium(II) nitrate (0.8 mg) in0.5 ml toluene. Ratio of monomer:procatalyst:activator was 100,000:1:2.The reaction was stirred for 3.5 hours at 55° C. during which time thereaction became a gel. The gel was dissolved in toluene. The product wasprecipitated in acetone and dried under vacuum to give 12.2 g, 61% ofwhite polymer. Mn (Daltons): 1,959,122, Mw (Daltons): 4,394,532,Polydispersity: 2.2. Incorporation of triethoxysilylnorbornene wasdemonstrated by ¹H NMR in C₆D₆.

EXAMPLE 169

To a solution of LiFABA (1.2 mg) and butylnorbornene (10.0 g) in toluene(total solution volume 60 ml) was added(allyl)(tricyclohexylphosphine)palladium(II) triflate (0.15 mg) in 1.0ml toluene. Ratio of monomer:procatalyst:activator was 250,000:1:5. Thereaction was stirred for 4 hours at 65° C. during which time thereaction became a rubbery solid. The solid was dissolved in toluene. Theproduct precipitated in acetone and dried under vacuum to give 5.0 g,50% of white polymer. Molecular weight of product was too high to bemeasured by available GPC techniques.

EXAMPLE 170

To a solution of LiFABA (1.2 mg) and butylnorbornene (9.9 g) andbutenylnorbornene (0.10 g) in toluene (total solution volume 60 ml) wasadded (allyl)(tricyclohexylphosphine)palladium(II) triflate (0.15 mg) in1.0 ml toluene. Ratio of monomer:procatalyst:activator was 250,000:1:5.The reaction was stirred for 4 hours at 65° C. during which time thereaction became a rubbery solid. The solid was dissolved in toluene. Theproduct precipitated in acetone and dried under vacuum to give 5.8 g,58% of white polymer. Mn (Daltons): 290,492, Mw (Daltons): 1,167,790,Polydispersity: 4.0.

EXAMPLE 171

To a solution of LiFABA (1.2 mg) and butylnorbornene (9.5 g) andbutenylnorbornene (0.50 g) in toluene (total solution volume 60 ml) wasadded (allyl)(tricyclohexylphosphine)palladium(II) triflate (0.15 mg) in1.0 ml toluene. Ratio of monomer:procatalyst:activator was 250,000:1:5.The reaction was stirred for 4 hours at 65° C. The product wasprecipitated in acetone and dried under vacuum to give 1.5 g, 15% ofwhite polymer. Mn (Daltons): 175,150, Mw (Daltons): 419,563,Polydispersity: 2.4.

EXAMPLE 172

To a solution of LiFABA (1.2 mg) and butylnorbornene (9.0 g) andbutenylnorbornene (1.0 g) in toluene (total solution volume 60 ml) wasadded (allyl)(tricyclohexylphosphine)palladium(II) triflate (0.15 mg) in1.0 ml toluene. Ratio of monomer:procatalyst:activator was 250,000:1:5.The reaction was stirred for 4 hours at 65° C. The product wasprecipitated in acetone and dried under vacuum to give 5.8 g, 58% ofwhite polymer. Mn (Daltons): 61,438, Mw (Daltons): 157,953,Polydispersity: 2.6.

EXAMPLE 173

To a solution of LiFABA (1.2 mg) and butylnorbornene (7.5 g) andbutenylnorbornene (2.5 g) in toluene (total solution volume 60 ml) wasadded 10 (allyl)(tricyclohexylphosphine)palladium(II) triflate (0.15 mg)in 1.0 ml toluene. Ratio of monomer:procatalyst:activator was250,000:1:5. The reaction was stirred for 4 hours at 65° C. The productwas precipitated in acetone and dried under vacuum to give 4.1 g, 41% ofwhite polymer. Mn (Daltons): 22,182, Mw (Daltons): 77,524,Polydispersity: 3.5.

EXAMPLE 174

To a solution of DANFABA (0.45 mg) and hexylnorbornene (10.0 g) intoluene (total solution volume was 33 ml) was added(allyl)(tricyclohexylphosphine)(perfluorophenyl)palladium(II) in 1.0 mltoluene. The reaction was stirred for 4 hours at 60° C., the product wasprecipitated in acetone and dried under vacuum to give a white polymer1.5 g (15%).

EXAMPLE 175

To a mixture of butylnorbornene (8.41 g, 56.1 mmol) and5-triethoxysilylnorbornene (1.59 g, 6.21 mmol) was added sodiumtetraphenylborate (0.4 mg, 0.0013 mmol). This mixture was diluted with32 ml of toluene. Approximately 50 μl of a toluene solution of(allyl)palladium chloride dimer (2.5 M) and 20 μl of a toluene solutionof tricyclohexylphosphine (12.5 mmol) was diluted to about 1 ml totalwith toluene and added to the monomer solution. The mixture was heatedto 65° C. for 4 hours. The resulting mixture was poured into acetone. Nopolymer precipitated.

EXAMPLE 176

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of butylnorbornene (4.59g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), silicagel (1.0 g, calcined at 220° C. for 24 hours followed by 600° C. for 5hours), and lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg,0.0016mmol). The contents were heated to 65° C. for 45 minutes and thenramped to 150° C. and held for 15 minutes. The contents were then cooledroom temperature. A very hard polymeric puck with suspended silicaparticles resulted.

EXAMPLE 177

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of butylnorbornene (4.59g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), silicagel (0.3 g, calcined at 220° C. for 24 hours followed by 600° C. for 5hours), and lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg,0.0016 mmol). The contents were heated to 65° C. for 45 minutes and thenramped to 150° C. and held for 15 minutes. The contents were then cooledroom temperature. A very hard polymeric puck with suspended silicaparticles resulted.

EXAMPLE 178

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of butylnorbornene (4.59g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), andlithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg, 0.0016 mmol).The contents were placed into a 150° C. bath and held for 30 minutes.The contents were then cooled room temperature. A very hard polymericpuck resulted.

EXAMPLE 179

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.04 mlaliquot of this solution was added to a mixture of butylnorbornene (9.18g, 61.2 mmol), 5-triethoxysilylnorbornene (0.82 g, 3.2 mmol), silica gel(2.00 g, calcined at 220° C. for 24 hours followed by 600° C. for 5hours), and lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg,0.0016 mmol). The contents were placed into a 150° C. bath and held for30 minutes. The contents were then cooled room temperature. A very hardpolymeric puck resulted with suspended silica particles.

EXAMPLE 180

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of hexylnorbornene (5.44g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), andlithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg, 0.0016 mmol).The mixture was allowed to stand at room temperature for 1.5 hours afterwhich time the solution became quite viscous. This mixture was thenpoured onto a silicon wafer. The wafer was heated to about 265° C. byramping the temperature from ambient to 170° C., then 200° C., then 225°C., then to 265° C. The wafer was then cooled and immersed in water tofacilitate removal of the transparent film. From thin film tensilemeasurements (ASTM D 1708-93), a modulus of 62,500±18,100 psi andelongation at break of 55±21%. No detectable monomer or toluene wasobserved by ¹H NMR measurements.

EXAMPLE 181

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of decylnorbornene (7.16g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), andlithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg, 0.0016 mmol).The mixture was allowed to stand at room temperature for 1.5 hours afterwhich time the mixture became slightly viscous. This mixture was thenpoured onto a silicon wafer. The wafer was then heated to about 170° C.The wafer was then cooled and immersed in water to facilitate removal ofa transparent film. No detectable monomer or toluene was observed by ¹HNMR measurements.

EXAMPLE 182

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of decylnorbornene (7.16g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), andlithium tetrakis(pentafluorophenyl)-borate·2.5Et₂O (1.4 mg, 0.0016mmol). Some of this mixture was then poured onto a silicon wafer. Thewafer was then heated to about 170° C. and held for 15 minutes. Thewafer was then cooled and immersed in water to facilitate removal of atransparent film. From thin film tensile measurements (ASTM D1708-93), amodulus of 11,600±1950 psi and elongation at break of 185±11%.

The rest of the mixture prepared above was allowed to stand for 7 daysat ambient temperature. The mixture became more viscous, yet mobile. Asecond film was cast onto a silicon wafer and heated identically to thatabove. From thin film tensile measurements (ASTM D1708-93), a modulus of8700±1040 psi and elongation at break of 158±24%.

EXAMPLE 183

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of decylnorbornene (7.06g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), exo,trans, exo-norbornadiene dimer (0.06 g, 0.33 mmol) and lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg, 0.0016 mmol). Afterallowing the mixture to stand for about an hour, it was poured onto asilicon wafer. The wafer was then heated to about 170° C. and held for30 minutes. The wafer was then cooled and immersed in water tofacilitate removal of a transparent film. From thin film tensilemeasurements (ASTM D1708-93), a modulus of 7600±640 psi and elongationat break of 100±3%.

EXAMPLE 184

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of decylnorbornene (7.06g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), Irgafos®168 (0.06 g, 0.33 mmol) and lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg, 0.0016 mmol). Afterallowing the mixture to stand for about two hours, it was poured onto asilicon wafer. The wafer was then heated to about 170° C. and held for30 minutes. The wafer was then cooled and immersed in water tofacilitate removal of a transparent film.

EXAMPLE 185

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of decylnorbornene (6.80g, 29.1 mmol), 5-triethoxysilylnorbornene (0.39 g, 1.60 mmol), exo,trans, exo-norbornadiene dimer (0.59 g, 3.2 mmol) and lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg, 0.0016 mmol). Themixture was poured onto a silicon wafer to form a thin film of solution.The mixture was then heated to about 170° C. and held for 30 minutes.The wafer was then cooled and immersed in water to facilitate removal ofthe transparent film. From thin film tensile measurements (ASTMD1708-93), a modulus of 12400±2450 psi and elongation at break of 42±6%.

EXAMPLE 186

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of decylnorbornene (5.73g, 24.5 mmol), 5-triethoxysilylnorbornene (0.37 g, 1.45 mmol), exo,trans, exo-norbornadiene dimer (1.18 g, 6.41 mmol) and lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (1.4 mg, 0.0016 mmol). Themixture was poured onto a silicon wafer to form a thin film. The mixturewas then heated to about 170° C. and held for 30 minutes. The wafer wasthen cooled and immersed in water to facilitate removal of thetransparent film. From thin film tensile measurements (ASTM D1708-93), amodulus of 43700 psi and elongation at break of 11%.

EXAMPLE 187

An 0.05 ml aliquot of a stock solution of(allyl)palladium(tricyclohexylphosphine)triflate (0.00623 M in toluene)was added to a mixture of hexyl norbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), and lithiumtetrakis(pentafluoro-phenyl)borate·2.5Et₂O (1.4 mg, 0.0016 mmol). Thismixture was then poured onto a silicon wafer to form a thin film ofsolution. The mixture was then heated to about 270° C. for 15 minutes.The wafer was then cooled and immersed in water to facilitate removal ofthe transparent film. From thin film tensile measurements (ASTMD1708-93), a modulus of 62,000±3400 psi and elongation at break of68±7%. Dynamic thermogravimetric analysis of the film (10° C./minute,from 35 to 460° C.) showed negligible weight loss at 350° C. (1.0%).

EXAMPLE 188

A stock solution of (allyl)palladium chloride dimer (0.00623 M) andtricyclohexylphosphine (0.0125 M) in toluene was prepared. An 0.05 mlaliquot of this solution was added to a mixture of decylnorbornene (7.16g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g, 1.60 mmol), andlithium tetrakis(pentafluorophenyl)-borate·2.5Et₂O (1.4 mg, 0.0016 mmol)which contained 6 weight percent barium titanate (Cabot). This mixturewas then poured onto a silicon wafer. The wafer was then heated to about170° C. and held for 30 minutes. The wafer was then cooled and immersedin water to facilitate removal of a film containing suspended bariumtitanate particles.

EXAMPLE 189

The above experiment was repeated except a 6 weight percent mixture oflead magnesium niobate-lead titanate (TAMTRON® Y5V 183U from TamCeramics) was used instead of barium titanate. An opaque, beige filmresulted.

EXAMPLE 190

Dimethylanilinium tetrakis(bis(3,5-trifluoromethyl)phenyl)borate (0.002g, 0.0016 mmol) was added to 5.44 g (30.6 mmol). To this mixture wasadded about 0.05 ml of a 0.00623 M solution of(allyl)palladium(tricyclohexylphosphine)(methyl) in toluene. Thismixture was poured onto a silicon wafer and heated to 270° C. for 15minutes. A thin film was recovered.

EXAMPLE 191

A stock solution of (allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) in toluene was prepared. An 0.05 ml aliquotof this solution was added to a mixture of decylnorbornene (7.16 g, 30.6mmol), 5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)-borate·2.5Et₂O (1.4 mg, 0.0016 mmol) whichcontained 40 weight percent of lead magnesium niobate (TAMTRON® Y5V183Ufrom Tam Ceramics). This mixture was then poured onto a silicon wafer.The mixture was then heated to about 180° C. and held for 30 minutes. Afilm containing the lead magnesium niobate was recovered after cooling.

EXAMPLE 192

Lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.0016 mmol)was added to hexylnorbornene (5.44 g, 30.6 mmol). To this mixture wasadded about 0.05 ml of a 0.00623 M solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate in toluene.This mixture was poured onto a silicon wafer and heated to 270° C. for30 minutes. A clear film was recovered.

EXAMPLE 193

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.1 ml aliquot of this solution was added to amixture of decylnorbornene (7.16 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)-borate·2.5Et₂O (2.8 mg, 0.0032 mmol) whichcontained 40 weight percent of barium titanate (Cabot). This mixture wasthen poured onto a silicon wafer. The mixture was then heated to about170° C. and held for 30 minutes. A film containing the barium titanatewas recovered after cooling.

EXAMPLE 194

A stock solution of{2-[(dimethylamino)methyl]phenyl-C,N-}palladium(tricyclohexyl-phosphine)triflate(0.00623 M). An 0.75 ml aliquot of this solution was added to a mixtureof hexylnorbornene (5.44 g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41g, 1.6 mmol), and lithium tetrakis(pentafluorophenyl)-borate·2.5 Et₂O(2.1 mg, 0.0025 mmol). This mixture was then poured onto a siliconwafer. The mixture was then heated to about 270° C. A film was recoveredafter cooling.

EXAMPLE 195

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.1 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)-borate·2.5 Et₂O (2.8 mg, 0.0032 mmol). Thismixture was then poured onto a silicon wafer. The mixture was thenheated to about 170° C. and held for 30 minutes. A film was recoveredafter cooling.

EXAMPLE 196

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.1 ml aliquot of this solution was added to amixture of hexylnorbornene (4.58 g, 25.7 mmol),5-triethoxysilylnorbornene (1.65 g, 6.45 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.8 mg, 0.0032 mmol). Thismixture was then poured onto a silicon wafer. The mixture was thenheated to about 270° C. and held for 15 minutes. A transparent film wasrecovered after cooling.

EXAMPLE 197

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.1 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.8 mg, 0.0032 mmol). Thismixture was then poured onto a silicon wafer. The mixture was thenheated to about 270° C. and held for 15 minutes. A film was recoveredafter cooling.

EXAMPLE 198

Approximately 0.18 ml of a deuterated benzene solution of(allyl)palladium(tricyclohexylphosphine)(methyl) (0.0072 M),N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (0.014 ml), anddiethyl ether (0.0072 ml) was added to a mixture of hexylnorbornene(5.44 g, 30.6 mmol) and 5-triethoxysilylnorbornene (0.41 g, 1.6 mmol),and lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.0032mmol) which had been sparged with air. This mixture was then poured ontoa silicon wafer. The mixture was then heated to about 170° C. and heldfor 30 minutes. A film was recovered after cooling.

EXAMPLE 199

A stock solution of (allyl)palladium(tricyclohexylphosphine)chloride(0.00623 M) in toluene was prepared. An 0.2 ml aliquot of this solutionwas added to a mixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol) whichhad been sparged with air. This mixture was then poured onto a siliconwafer. The mixture was then heated to about 170° C. and held for 15minutes. A film was recovered after cooling. Dynamic thermogravimetricanalysis of the film (10° C./minute, from 35 to 460° C.) showednegligible weight loss at 350° C. (2.0%).

EXAMPLE 200

A stock solution of (allyl)palladium(tricyclohexylphosphine)chloride(0.00623 M) in toluene was prepared. An 0.1 ml aliquot of this solutionwas added to a mixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0013 mmol) whichhad been sparged with air. This was then heated to about 170° C. andheld for 4 hours. A hard polymer puck was recovered after cooling.

EXAMPLE 201

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.2 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol) whichhad been sparged with air. This mixture was then poured onto a siliconwafer. The mixture was then heated to about 170° C. and held for 15minutes. A film was recovered after cooling which had a thickness ofabout 20 mils. Dynamic thermogravimetric analysis of the film (10°C./minute, from 35 to 460° C.) showed negligible weight loss at 350° C.(0.9%).

EXAMPLE 202

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.1 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.1 mg, 0.0013 mmol) whichhad been sparged with air. This mixture was heated to about 170° C. andheld for 4 hours. A hard polymeric puck was recovered after cooling.

EXAMPLE 203

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.5 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-glycidylether-2-norbornene (0.24 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (5.6 mg, 0.0067 mmol) whichhad been sparged with air. This mixture was then poured onto a siliconwafer in air. The mixture was then heated to about 170° C. and held for15 minutes. A film was recovered after cooling.

EXAMPLE 204

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.5 ml aliquot of this solution was added to amixture of hexylnorbornene (4.58 g, 25.7 mmol),5-glycidylether-2-norbornene (0.97 g, 6.4 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (5.6 mg, 0.0067 mmol) whichhad been sparged with air. This mixture was then poured onto a siliconwafer in air. The mixture was then heated to about 170° C. and held for15 minutes. A film was recovered after cooling.

EXAMPLE 205

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.83 ml aliquot of this solution was added to amixture of hexylnorbornene (10.9 g, 61.1 mmol) and5-triethoxysilylnorbornene (0.82 g, 3.2 mmol). To a separate vial wasadded lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (9.0 mg, 0.011mmol), hexylnorbornene (10.9 g, 61.1 mmol) and5-triethoxysilylnorbornene (0.82 g, 3.2 mmol). Each mixture was spargedwith air. Equal volumes of solution from each vial were mixed and thenpoured onto a silicon wafer in air. The mixture was then heated to about170° C. and held for 15 minutes. A transparent film resulted. Dynamicthermogravimetric analysis of the film (10° C./minute, from 35 to 460°C.) showed negligible weight loss at 350° C. (0.9%). The vials were thenstored at ambient temperature in air. After 3 days, more of the solutionwas cast in the same manner. A transparent film resulted. Dynamicthermogravimetric analysis of the film (10° C./minute, from 35 to 460°C.) showed negligible weight loss at 350° C. (2.0%). The vials werestored again at ambient temperature in air. After 4 more days, more ofthe solution was cast in the same manner. A transparent film resulted.Dynamic thermogravimetric analysis of the film (10° C./minute, from 35to 460° C.) showed still negligible weight loss at 350° C. (2.7%).

EXAMPLE 206

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.0.10 ml aliquot of this solution was added toa mixture of hexylnorbornene (10.9 g, 61.1 mmol),5-triethoxysilylnorbornene (0.82 g, 3.2 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), whichhad been saturated with disperse red number 1. This mixture was thenfiltered through a 0.2 μm filter and then was poured onto a siliconwafer in air. The mixture was then heated to about 170° C. and held for15 minutes. A colored, transparent film resulted.

EXAMPLE 207

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.0.10 ml aliquot of this solution was added toa mixture of hexylnorbornene (10.9 g, 61.1 mmol),5-triethoxysilylnorbornene (0.82 g, 3.2 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), whichhad been saturated with disperse orange number 1. This mixture was thenfiltered through a 0.2 μm filter and then was poured onto a siliconwafer in air. The mixture was then heated to about 170° C. and held for15 minutes. A colored, transparent film resulted.

EXAMPLE 208

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.0.10 ml aliquot of this solution was added toa mixture of hexylnorbornene (10.9 g, 61.1 mmol),5-triethoxysilylnorbornene (0.82 g, 3.2 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), whichhad been saturated with disperse blue number 14. This mixture was thenfiltered through a 0.2 μm filter and then was poured onto a siliconwafer in air. The mixture was then heated to about 170° C. and held for15 minutes. A colored, transparent film resulted.

EXAMPLE 209

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.0.10 ml aliquot of this solution was added toa mixture of hexylnorbornene (10.9 g, 61.1 mmol),5-triethoxysilylnorbornene (0.82 g, 3.2 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), whichhad been saturated with disperse yellow number 7. This mixture was thenfiltered through a 0.2 μm filter and then was poured onto a siliconwafer in air. The mixture was then heated to about 170° C. and held for15 minutes. A colored, transparent film resulted.

EXAMPLE 210

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.0.10 ml aliquot of this solution was added toa mixture of hexylnorbornene (10.9 g, 61.1 mmol),5-triethoxysilylnorbornene (0.82 g, 3.2 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), whichhad been saturated with copper naphthalocyanine. This mixture was thenfiltered through a 0.2 μm filter and then was poured onto a siliconwafer in air. The mixture was then heated to about 170° C. and held for15 minutes. A colored, transparent film resulted.

EXAMPLE 211

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.2 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), andweight percent Kraton® G1652. This mixture was then poured onto asilicon wafer in air. The wafer was then heated to about 170° C. andheld for 15 minutes. A slightly opaque film was recovered after cooling.

EXAMPLE 212

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.2 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), and 10weight percent Kraton® G1652. This mixture was then poured onto asilicon wafer in air. The wafer was then heated to about 170° C. andheld for 15 minutes. A markedly opaque film was recovered after cooling.

EXAMPLE 213

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.2 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), and 2weight percent Kraton® 1101. This mixture was then poured onto a siliconwafer in air. The film was then heated to about 170° C. and held for 15minutes. An opaque film was recovered after cooling.

EXAMPLE 214

A stock solution of(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00623 M) intoluene was prepared. An 0.2 ml aliquot of this solution was added to amixture of hexylnorbornene (5.44 g, 30.6 mmol),5-triethoxysilylnorbornene (0.41 g, 1.6 mmol), and lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.2 mg, 0.0026 mmol), and 2weight percent Kraton® 1726. This mixture was then poured onto a siliconwafer in air. The wafer was then heated to about 170° C. and held for 15minutes. A transparent film was recovered after cooling.

EXAMPLE 215

To a mixture of norbornene (4.84 g, 51.5 mmol) and5-triethoxysilylnorbornene (3.30 g, 12.9 mmol) was added lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.8 mg, 0.0032 mmol). Tothis mixture was added (allyl)palladium(tricyclohexylphosphine)triflate(0.10 ml of a 0.0062 M solution in toluene). This mixture was allowed tostand at room temperature until it became viscous. It was then poured,in air, onto a silicon wafer. The wafer ramped up to 170° C. over 20minutes and then held at this temperature for an additional 5 minutes. Afilm was recovered after cooling the wafer.

EXAMPLE 216

In air, lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (3.3 mg,0.0038 mmol) was dissolved in 5.5 g of ethylnorbornene (45 mmol) and0.61 g of 5-triethoxysilylnorbornene (2.4 mmol). To this mixture wasadded (allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.30 mlof a 0.0062 M solution in toluene). The mixture was cast onto a siliconwafer in air and heated to 170° C. for 20 minutes. A transparent filmresulted.

EXAMPLE 217

A stock solution of(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.00623 M)in toluene was prepared. Lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.0064 mmol) was weighed into a bottle. This bottle wasopened to the ambient air and 5-triethoxysilylnorbornene (8.26 g, 32.2mmol) was added to this bottle. Then, 0.52 ml of the palladium stocksolution was added to the bottle containing the lithium salt and themonomer. This solution was heated to 46° C. with stirring while leadmagnesium niobate-lead titanate (6.56 g, TAMTRON® Y5V183U from TamCeramics) was added. The mixture was heated at 70° C. and stirred at 300rpm for 7.5 minutes. Then the contents were poured onto an oxidizedsilicon wafer that had been coated with an 8000 Å thick aluminum metallayer. This wafer was heated to 170° C. for 15 minutes. The wafer wasquenched in water. While the aluminum delaminated from the silicon waferthe film continued to adhere to the aluminum film indicating goodadhesion of the polymer to the aluminum metal.

The permittivity of the film averaged 5.0 over 1 MHz to 1.1 GHzfrequency range, while the loss tangent averaged 0.016 over the samefrequency range.

EXAMPLE 218

A stock solution of (allyl)palladium(tricyclohexylphosphine)(triflate)(0.00623 M) in toluene was prepared. Lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.0089 grams) was weighedinto a bottle. This bottle was opened to the ambient air and5-triethoxysilylnorbornene (10.18 g, 39.7 mmol) was added to thisbottle. Then 0.15 ml of palladium stock solution was added to the bottlecontaining the lithium salt and the monomer. This mixture was heated to52° C. with stirring (100 to 500 rpm) while lead magnesium niobate-leadtitanate (24.43 g, TAMTRON® Y5V183U from Tam Ceramics) was added. After8.5 minutes at 52° C., the solution was ramped to 70° C. in 3 minutes.

After dwelling for 4.5 minutes at 70° C., the mixture was poured fromthe bottle into a 3 inch diameter ring resting on top of a 4 inchoxidized silicon wafer coated with 8000 Å of aluminum (aluminum had beencoated by evaporation). The wafer was ramped from 70° C. to 170° C. in 4minutes. The mixture was heated for 15 minutes at 170° C. Then, thewafer and ring were removed from the hotplate and quenched in water. Asthe film contracted, due to its exposure to lukewarm water, the aluminumdelaminated from the wafer, but the aluminum remained adhered to thefilm. This indicates that the adhesion of aluminum is better to the filmproduced than to the thin (8000 Angstroms) layer of silicon dioxide ontop of the silicon wafer.

The permittivity of the film averaged 9.8 over 1 MHz to 1.1 GHzfrequency range, while the loss tangent averaged 0.023 over the samefrequency range.

EXAMPLE 219

A stock solution of(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.0249 M) inmethylene chloride was prepared. Lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.011 grams) was weighedinto a bottle. This bottle was opened to the ambient air and5-triethoxysilylnorbornene (8.24 g, 32.2 mmol) was added to the bottle.Approximately 0.26 ml of the catalyst stock solution was added to theabove mixture. The mixture was allowed to stir at 90° C. for about 1minute, then lead magnesium niobate-lead titanate (32.96 g, TAMTRON®Y5V183U from Tam Ceramics) was added. The mixture was allowed to stirfor an additional 10 minutes at 90° C. The mixture was then poured ontopolyimide film and heated to 90° C. for 15 minutes and then heated to180° C. for 30 minutes. A composite film resulted.

The permittivity of the film averaged 15.8 over 1 MHz to 1.1 GHzfrequency range, while the loss tangent averaged 0.016 over the samefrequency range.

EXAMPLE 220

A stock solution of(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.0249 M) inmethylene chloride was prepared. Lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.011 g) was weighed into abottle. This bottle was opened to the ambient air and5-triethoxysilylnorbornene (8.24 g, 32.2 mmol) was added to the bottle.Approximately 0.26 ml of the catalyst stock solution was added to theabove mixture. The mixture was allowed to stir at 90° C. for about 1minute, then lead magnesium niobate-lead titanate (24.72 g, TAMTRON®Y5V183U from Tam Ceramics) was added. The mixture was allowed to stirfor an additional 10 minutes at 90° C. The mixture was then poured ontopolyimide film and heated to 90° C. for 15 minutes and then heated to180° C. for 30 minutes. A composite film resulted.

The permittivity of the film averaged 10.8 over 1 MHz to 1.1 GHzfrequency range, while the loss tangent averaged 0.014 over the samefrequency range.

EXAMPLE 221

Hexylnorbornene (10.88 g, 61.1 mmol), 5-triethoxysilylnorbornene (0.82g, 3.2 mmol), and lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O(0.01 1 g, 0.013 mmol) were combined in air. Approximately 0.51 ml of a0.0125 M stock solution of(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.0064 mmol)in toluene was added to the monomer mixture. Next, 35.1 g of leadmagnesium niobate-lead titanate (24.72 g, TAMTRON® Y5V183U from TamCeramics) was added with vigorous stirring. The mixture was heated to90° C. for about 10 minutes. After pouring the resulting mixture onto asilicon wafer, the mixture was heated to 90° C. for 15 minutes and thento 180° C. for 30 minutes. A composite film resulted.

The permittivity of the film averaged 6.8 over 1 MHz to 1.1 GHzfrequency range, while the loss tangent averaged 0.002 over the samefrequency range.

EXAMPLE 222

Lead magnesium niobate-lead titanate (24.72 g, TAMTRON® Y5V183U from TamCeramics) was crushed in a Siebtechnik reciprocating grinder for 1minute. Then a solution of 5-triethoxysilylnorbornene (8.24 g, 32.2mol), lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.011 grams,0.013 mmol), and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.0064 mmol)was added to the lead magnesium niobate-lead titanate. The mixture wasmilled for an additional 3 minutes. The resulting smooth paste wasspread onto a glass plate with a doctor blade with a setting of 20 mils.The plate was placed under vacuum and heated to 250° C. over 75 minutesand held at held for 1 hour. Then the plate was cooled under vacuumovernight to give thin composite film was a smooth surface. Examinationof cross-sectioned film revealed homogeneous dispersion of thecomposite.

EXAMPLE 223

Hexylnorbornene (5.44 g, 31.0 mmol), 5-triethoxynorbornene (0.41 g, 1.6mol), and lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg,0.0032 mmol) were mixed together in air. To this mixture was added(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.00064mmol) as a stock solution (0.0249 ml) in methylene chloride. Theresulting mixture was heated to 70° C. for about 10 minutes untilsignificant thickening of the solution was observed. The mixture wasthen poured onto a glass plate and drawn with a doctor blade. The platewas placed in an oven and slowly ramped to 140° C. and held there for 1hour. After cooling, the thin film was removed from the glass plate withthe aid of cool water. A transparent film measuring about 7 mils thickwas recovered. The thickness of the film can be adjusted by changing thedoctor blade setting.

EXAMPLE 224

Hexylnorbornene (5.44 g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g,1.6 mmol), and divinyl-terminated polydimethylsiloxane (0.31 g, GelestDMS-VO5), and lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg,0.0032 mmol) were combined in air. Approximately 0.10 ml of a 0.0062 Mtoluene solution of(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.00062mmol). The mixture was then poured onto a silicon wafer and heated to90° C. for 15 minutes and then heated to 170° C. for 15 minutes. Atransparent film was recovered.

EXAMPLE 225

The experiment was carried out as in the above example, except thatdifferent polydimethylsiloxanes were used.

a. Divinyl-terminated polydimethylsiloxane (0.31 g, Gelest DMS-V22,Mn=9400) was used. A very opaque, almost white film was recovered.

b. Divinyl-terminated polydimethylsiloxane (0.31 g, Gelest DMS-V00,Mn=186) was used. A transparent film was recovered.

c. Dimethyl-terminated polydimethylsiloxane (0.31 g, Gelest DMS-T05,Mn=770) was used. A transparent film was recovered.

d. Divinyl-terminated polydimethyldiphenylsiloxane (0.31 g, GelestPDV-1625, Mn=9500) was used. An opaque film was recovered.

e. Divinyl-terminated polydimethylmonomethylmonovinylsiloxane (0.31 g,Gelest VMM-010) was used. An opaque film was recovered.

EXAMPLE 226

a. Hexylnorbornene (5.44 g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41g, 1.6 mmol), and divinyl-terminated polydimethylsiloxane (0.31 g,Gelest DMS-V22, Mn=9400), and lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.0032 mmol) werecombined in air. Approximately 0.10 ml of a 0.0062 M methylene chloridesolution of allyl)palladium(tricyclohexylphosphine)(trifluoroacetate)(0.00062 mmol). The mixture was heated to 80° C. for about 10 minutesuntil it became somewhat viscous. The mixture was then poured onto aglass plate and spread with a doctor blade set a 14 mils. The plate washeated to 90° C. under vacuum and held for 30 minutes. Then the platewas heated to 170° C. and held for 15 minutes. An opaque film wasrecovered.

b. Hexylnorbornene (5.44 g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41g, 1.6 mmol), and divinyl-terminated polydimethylsiloxane (0.31 g,Gelest DMS-V00, Mn=186), and lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.0032 mmol) werecombined in air. Approximately 0.10 ml of a 0.0062 M methylene chloridesolution of (allyl)palladium(tricyclohexylphosphine)(trifluoroacetate)(0.00062 mmol). The mixture was heated to 80° C. for about 10 minutesand it became somewhat viscous. The mixture was then poured onto a glassplate and spread with a doctor blade set at 14 mils. The plate washeated to 90° C. under vacuum and held for 30 minutes. Then the platewas heated to 170° C. and held for 15 minutes. A transparent film wasrecovered.

EXAMPLE 227

Hexylnorbornene (5.44 g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g,1.6 mmol), tetracyclododecadiene (0.27 g), Irganox® 1076 (0.03 g),divinyl-terminated polydimethylsiloxane (0.32 g, Gelest DMS-V05,Mn=770), and lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg,0.0064 mmol) were combined in air. The mixture was briefly sonicated toaid in dissolution of the antioxidant. Approximately 0.054 ml of a 0.025M methylene chloride solution of(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.0014mmol). The mixture was heated to 80° C. for about 5 minutes and itbecame somewhat viscous. The mixture was then poured onto a glass plateand spread with a doctor blade set at 16 mils. The plate was heated to75° C. under vacuum and held for 20 minutes. Then the plate was heatedto 150° C. and held for 10 minutes. A transparent film was recovered.

EXAMPLE 228

Hexylnorbornene (5.44 g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41 g,1.6 mmol), and sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate(2.9 mg, 0.0032 mmol) were combined in air. Approximately 0.10 ml of a0.0062 M toluene solution of(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.00062mmol). The mixture was then poured onto a silicon wafer and heated to90° C. for 15 minutes and then heated to 170° C. for 15 minutes. Atransparent film was recovered.

EXAMPLE 229

A. Hexylnorbornene (5.44 g, 30.6 mmol), 5-triethoxysilylnorbornene (0.41g, 1.6 mmol), and lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (1.5mg, 0.0016 mmol), and 0.10 ml of a 0.0031 M stock solution of(allyl)palladium(tricyclohexylphosphine)(triflate) in toluene (0.00031mmol) were combined in air in a Class 1000 clean room. The mixture wasthen filtered through a 0.2 μ Teflon® frit with the aid of a syringeinto a clean test tube. The test tube was then heated to 90° C. held for30 minutes and then ramped up to 170° C. and held for 1 hour. The testtube was cooled and the ends of the polymeric cylinder were cut off andpolished with #4000 sandpaper to give a completely transparent cylinderof 5 cm length.

B. The above experiment was repeated, except that the following amountsof cocatalyst and catalyst were used: lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (0.9 mg, 0.0011 mmol), and0.07 ml of a 0.0031 M stock solution of(allyl)palladium(tricyclohexylphosphine)(triflate) in toluene (0.00022mmol). The test tube was cooled and the ends of the polymeric cylinderwere cut off and polished with #4000 sandpaper to give a completelytransparent cylinder of 5 cm length.

EXAMPLE 230

Butylnorbornene (5.90 g, 39 mmol) and triethoxysilylnorbornene (0.53 g,2.1 mmol) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (0.9 mg, 0.0011 mmol) in avial. (Allyl)palladium(triisopropylphosphine)(triflate) (0.00021 mmol)in 67 μl of toluene was added to the vial. The vial was heated to 270°C. for 15 minutes to yield a hard plug of polymer.

EXAMPLE 231

Hexylnorbornene (5.44 g) and triethoxysilylnorbornene (0.41 g) werecombined with lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (0.9 mg,0.0011 mmol) in a vial in air. To this mixture was added(allyl)palladium(tricyclohexylphosphine)(triflate) (0.00022 mmol) from a0.0031 M solution in toluene. The vial was heated to 90° C. for 30minutes and then to 230° C. for 30 min. A clear polymer rod resulted.

EXAMPLE 232

Hexylnorbornene (5.44 g) and triethoxysilylnorbornene (0.41 g) werecombined with lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (0.7 mg,0.0008 mmol) in a vial in air. To this mixture was added(allyl)palladium(tricyclohexylphosphine)(triflate) (0.00016 mmol) from a0.0031 M solution in toluene. The vial was heated to 90° C. for 30minutes and then to 230° C. for 30 min. A clear polymer rod resulted.

EXAMPLE 233

Hexylnorbornene (5.44 g) and triethoxysilylnorbornene (0.41 g) werecombined with lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (0.6 mg,0.0006 mmol) in a vial in air. To this mixture was added(allyl)palladium(tricyclohexylphosphine)(triflate) (0.00013 mmol) from a0.0031 M solution in toluene. The vial was heated to 90° C. for 30minutes and then to 230° C. for 30 min. A clear polymer rod resulted.

EXAMPLE 234

Hexylnorbornene (4.3 g, 24 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and ethylester of 5-norbornene carboxylic acid (1.07 g, 6.4 mmol)were combined with lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O(1.1 mg, 0.013 mmol) in a vial. To this mixture was added(allyl)palladium(trinaphthylphosphine)(triflate) (0.0064 mmol) from a0.013 M solution in toluene. The mixture was then poured onto a siliconwafer, heated to 90° C. for 15 minutes and then to 180° C. for 30minutes. A film resulted that showed only 2.7 percent weight loss at350° C. by TGA (10°/min).

EXAMPLE 235

Triethoxysilylnorbornene (8.24 g, 32 mmol) and lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (11 mg, 0.013 mmol) were mixedin a vial. To this mixture was added(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (0.0064 mmol)from a 0.013 M solution in toluene. The mixture was then poured onto apolyimide film, heated to 90° C. for 15 minutes and then to 180° C. for30 minutes. A film resulted that showed only 7.2 percent weight loss at350° C. by TGA (10°/min).

EXAMPLE 236

Hexylnorbornene (5.16 g, 29 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and benzylether of 5-norbornene methanol (0.34 g, 1.6 mmol) werecombined with lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (14 mg,0.016 mmol) were mixed together. The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00032 mmol,0.13 ml of a 0.025 M solution in methylene chloride), was added to themixture. The mixture was poured onto a silicon wafer and heated to 90°C. for 15 minutes and then to 170° C. for 15 minutes. A transparent filmresulted.

EXAMPLE 237

Hexylnorbornene (5.16 g, 29 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and phenylnorbornene (0.27 g, 1.6 mmol) were combined withlithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (14 mg, 0.016 mmol).The catalyst, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate(0.00032 mmol, 0.13 ml of a 0.025 M solution in methylene chloride), wasadded to the mixture. The mixture was poured onto a silicon wafer andheated to 90° C. for 15 minutes and then to 170° C. for 15 minutes. Afilm resulted.

EXAMPLE 238

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Trilene® CP30 (Uniroyal Chemical Co.) (0.31 g) were combinedwith lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.00032mmol) were mixed together. The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00064 mmol,26 μl of a 0.025 M solution in methylene chloride), was added to themixture. The mixture was poured onto a silicon wafer and heated to 90°C. for 15 minutes and then to 170° C. for 15 minutes. An opaque filmresulted.

EXAMPLE 239

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Trilene® CP40 (Uniroyal Chemical Co.) (0.31 g) were combinedwith lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.00032mmol). The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00064 mmol,26 μl of a 0.025 M solution in methylene chloride), was added to themixture. The mixture was poured onto a silicon wafer and heated to 90°C. for 15 minutes and then to 170° C. for 15 minutes. An opaque filmresulted.

EXAMPLE 240

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Trilene® CP50 (Uniroyal Chemical Co.) (0.31 g) were combinedwith lithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.00032mmol) were mixed together. The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00064 mmol,26 μl of a 0.025 M solution in methylene chloride), was added to themixture. The mixture was poured onto a silicon wafer and heated to 90°C. for 15 minutes and then to 170° C. for 15 minutes. An opaque filmresulted.

EXAMPLE 241

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 01.6 mmol), and Vistanex® LM-H-LC (Exxon) (0.12 g) were combined withlithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.00032 mmol)were mixed together. The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00064 mmol,50 μl of a 0.013 M solution in methylene chloride), was added to themixture. The mixture was poured onto a silicon wafer and heated to 90°C. for 15 minutes and then to 170° C. for 15 minutes. A clear filmresulted.

EXAMPLE 242

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Vistanex® LM-MH (Exxon) (0.12 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.00032 mmol). Thecatalyst, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate(0.00064 mmol, 50 μl of a 0.013 M solution in methylene chloride), wasadded to the mixture. The mixture was poured onto a silicon wafer andheated to 90° C. for 15 minutes and then to 170° C. for 15 minutes. Aclear film resulted.

EXAMPLE 243

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Vistanex® MML-100 (Exxon) (0.12 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.00032 mmol) weremixed together. The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.000064 mmol,50 μl of a 0.013 M solution in methylene chloride), was added to themixture. The mixture was poured onto a silicon wafer and heated to 90°C. for 15 minutes and then to 170° C. for 15 minutes. A hazy filmresulted.

EXAMPLE 244

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Vistanex® MML-140 (Exxon) (0.12 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (2.8 mg, 0.00032 mmol). Thecatalyst, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate(0.00064 mmol, 50 μl of a 0.013 M solution in methylene chloride), wasadded to the mixture. The mixture was poured onto a silicon wafer andheated to 90° C. for 15 minutes and then to 170° C. for 15 minutes. Ahazy film resulted.

EXAMPLE 245

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), tetracyclododecadiene (0.27 g, 1.7 mmol) and Vistanex® LM-H-LC(Exxon) (0.12 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.00064 mmol) weremixed together. The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00013 mmol,0.10 ml of a 0.013 M solution in methylene chloride), was added to themixture. The mixture was allowed to thicken in viscosity by standing atroom temperature for about 30 minutes in air. The mixture was thenpoured onto a glass plate and pulled into a film using a doctor blade.The plate was placed into an oven at 65° C. for 30 minutes and then intoan oven heated to 120° C. for 30 minutes under a slight vacuum. A clearfilm resulted. Using ASTM D1938-94, the film demonstrated an averagetear force of 29.4 g at 0.18 mm thickness.

EXAMPLE 246

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), tetracyclododecadiene (0.27 g, 1.7 mmol) and Vistanex® LM-MH(Exxon) (0. 12 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.00064 mmol). Thecatalyst, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate(0.00013 mmol, 0.10 ml of a 0.013 M solution in methylene chloride), wasadded to the mixture. The mixture was allowed to thicken in viscosity bystanding at room temperature for about 30 minutes in air. The mixturewas then poured onto a glass plate and pulled into a film using a doctorblade. The plate was placed into an oven at 65° C. for 30 minutes andthen into an oven heated to 120° C. for 30 minutes under a slightvacuum. A clear film resulted. Using ASTM D1938-94, the filmdemonstrated an average tear force of 21.6 g at 0.16 mm thickness.

EXAMPLE 247

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), tetracyclododecadiene (0.27 g, 1.7 mmol) and Vistanex® LM-H-LC(Exxon) (0.24 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.00064 mmol) weremixed together. The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00013 mmol,0.10 ml of a 0.013 M solution in methylene chloride), was added to themixture. The mixture was poured onto a silicon wafer and heated to 80°C. for 15 minutes and then heated to 170° C. for 15 minutes. A clearfilm resulted.

EXAMPLE 248

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), tetracyclododecadiene (0.27 g, 1.7 mmol) and Vistanex® LM-MH(Exxon) (0.24 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.00064 mmol). Thecatalyst, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate(0.00013 mmol, 0.10 ml of a 0.013 M solution in methylene chloride), wasadded to the mixture. The mixture was poured onto a silicon wafer andheated to 80° C. for 15 minutes and then heated to 170° C. for 15minutes. A clear film resulted.

EXAMPLE 249

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Vistanex® LM-MH (Exxon) (0.12 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.00064 mmol) weremixed together. The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00013 mmol,100 μl of a 0.013 M solution in methylene chloride), was added to themixture. The mixture was allowed to stand at room temperature until theviscosity increased. Then the mixture was poured onto a glass plate andpulled into a film using a doctor blade. The film was heated to 70° C.for 30 minutes and then to 120° C. for 30 minutes under a slight vacuum.The resulting film was transparent. Using ASTM D1938-94, the filmdemonstrated an average tear force of 31.9 g at 0.15 mm thickness.

EXAMPLE 250

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Vistanex® LM-H-LC (Exxon) (0.12 g) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.00064 mmol). Thecatalyst, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate(0.00013 mmol, 100 μl of a 0.013 M solution in methylene chloride), wasadded to the mixture. The mixture was allowed to stand at roomtemperature until the viscosity increased. Then the mixture was pouredonto a glass plate and pulled into a film using a doctor blade. The filmwas heated to 70° C. for 30 minutes and then to 120° C. for 30 minutesunder a slight vacuum. The resulting film was transparent. Using ASTM D1938-94, the film demonstrated an average tear force of 20.5 g at 0.1 1mm thickness. The film exhibited 1.6% weight loss at 325° C.

EXAMPLE 251

Hexylnorbornene (5.44 g, 31 mmol), triethoxysilylnorbornene (0.41 g, 1.6mmol), and Vistanex® LM-MS-LC (Exxon) (0.12 g) were combined withlithium tetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.00064mmol). The catalyst,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.00013 mmol,100 μl of a 0.013 M solution in methylene chloride), was added to themixture. The mixture was allowed to stand at room temperature until theviscosity increased. Then the mixture was poured onto a glass plate andpulled into a film using a doctor blade. The film was heated to 70° C.for 30 minutes and then to 120° C. for 30 minutes under a slight vacuum.The resulting film was transparent. Using ASTM D1938-94, the filmdemonstrated an average tear force of 39.9 g at 0.15 mm thickness.

EXAMPLE 252

Hexylnorbornene (5.44 g, 29 mmol) and 5-norbornene methanol (0.20 g, 1.6mmol) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O (5.6 mg, 0.00064 mmol). Thecatalyst, (allyl)palladium(tricyclohexylphosphine)trifluoroacetate(0.00013 mmol, 100 μl of a 0.013 M solution in methylene chloride), wasadded to the mixture. The mixture was poured onto a silicon wafer in theair and heated to 90° C. for 30 minutes then to 170° C. for 15 minutes.A clear film resulted.

EXAMPLE 253

Hexylnorbornene, triethoxysilylnorbornene, benzylether of 5-norbornenemethanol, and tetracyclododecene in an 85:5:5:5 molar ratio,respectively, were mixed together along with lithiumtetrakis(pentafluorophenyl)borate·2.5Et₂O. Ferrocene was added to thismixture until a saturation solution was obtained. To this mixture wasadded the catalyst,allyl)palladium(tricyclohexylphosphine)trifluoroacetate. The finalmonomers to catalyst to cocatalyst molar ratio was 25,000:1:2,respectively. The mixture was poured onto a silicon wafer andpolymerized to give an orange-colored disk.

EXAMPLE 254

Component A was prepared by combining hexylnorbornene (28.1 mmol),triethoxysilylnorbornene (3.3 mmol), norbornadiene dimer (1.6 mmol), and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.3×10⁻⁶ml). Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (3.0 mg, 3.4×10⁻⁶ ml) intriethoxysilylnorbornene (3.3 mmol) followed by addition ofhexylnorbornene (28.1 mmol), norbornadiene dimer (1.6 mmol). 6 ml ofcomponent A and 6 ml of component B were separately drawn intoindividual glass syringes, and combined after filtration through a 0.2micron filter disk. The combined mixture was cast onto 7″×9″ area ofglass. The mixture was heated at 65° C. for 30 minutes, and cured at180° C. for 1 hour leaving an optically transparent, odorless thin film.

EXAMPLE 255

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.9×10⁻⁶ml). A 3 wt % blend was prepared by dissolving 0.26 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=360,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 mmol) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. A 3 wt % blend was prepared by dissolving 0.26 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=360,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation. The film exhibited 3.5% weightloss at 325° C.

EXAMPLE 256

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.9×10⁻⁶mol). A 5 wt % blend was prepared by dissolving 0.43 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=360,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 mmol) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. A 5 wt % blend was prepared by dissolving 0.43 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=360,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation. The film exhibited 5.6% weightloss at 325° C.

EXAMPLE 257

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate)(1.9×10⁻⁶ ml).A 7 wt % blend was prepared by dissolving 0.60 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=360,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 ml) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. A 7 wt % blend was prepared by dissolving 0.60 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=360,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation.

EXAMPLE 258

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate)(1.9×10⁻⁶ ml).A 10 wt % blend was prepared by dissolving 0.85 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=270,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 mmol) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. A 10 wt % blend was prepared by dissolving 0.85 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=270,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation. The film exhibited 3.5% weightloss at 325° C.

EXAMPLE 259

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate)(1.9×10⁻⁶ ml).A 6 wt % blend was prepared by dissolving 0.50 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=270,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 mmol) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. A 6 wt % blend was prepared by dissolving 0.50 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=270,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation. The film exhibited 2.7% weightloss at 325° C.

EXAMPLE 260

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.9×10⁻⁶ml). A 3 wt % blend was prepared by dissolving 0.26 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=270,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 mmol) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. A 3 wt % blend was prepared by dissolving 0.26 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=270,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation. The film exhibited 2.5% weightloss at 325° C.

EXAMPLE 261

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.9×10⁻⁶ml). A 12 wt % blend was prepared by dissolving 1.18 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=208,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 mmol) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. A 12 wt % blend was prepared by dissolving 1.18 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=208,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation. The film exhibited 3.0% weightloss at 325° C.

EXAMPLE 262

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.9×10⁻⁶ml). A 8 wt % blend was prepared by dissolving 0.75 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=208,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 mmol) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. An 8 wt % blend was prepared by dissolving 0.75 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=208,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation. The film exhibited 3.7% weightloss at 325° C.

EXAMPLE 263

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.6 mmol), tetracyclododecene (2.3 mmol), 0.09g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.9×10⁻⁶ml). A 4 wt % blend was prepared by dissolving 0.36 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=208,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.6 mmol) followed by addition ofhexylnorbornene (39.3 mmol), tetracyclododecene (2.3 mmol), and 0.09 gIrganox® 1076. A 4 wt % blend was prepared by dissolving 0.36 g of a90:10 hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=208,000)into component B. 6 ml of viscous component A and 6 ml of viscouscomponent B were separately drawn into individual glass syringes, andcombined. The combined solution was cast onto 7″×9″ area of glass. Themixture was heated at 65° C. for 30 minutes, and cured at 180° C. for 1hour leaving an optically transparent, odorless thin film havingdimple-like regions of phase separation. The film exhibited 3.7% weightloss at 325° C.

EXAMPLE 264

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (4.4 mmol), 0.09 g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.9×10⁻⁶ml). A 6 wt % blend was prepared by dissolving 0.75 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=270,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.7 mg, 5.4×10⁻⁶ ml) intriethoxysilylnorbornene (4.4 mmol) followed by addition ofhexylnorbornene (39.3 mmol), and 0.09 g Irganox® 1076. A 6 wt % blendwas prepared by dissolving 0.75 g of a 90:10hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=270,000) intocomponent B. 6 ml of viscous component A and 6 ml of viscous component Bwere separately drawn into individual glass syringes, and combined. Thecombined solution was cast onto 7″×9″ area of glass. The mixture washeated at 65° C. for 30 minutes, and cured at 180° C. for 1 hour leavingan optically transparent, odorless thin film having dimple-like regionsof phase separation. The film exhibited 1.7% weight loss at 325° C.

EXAMPLE 265

Component A was prepared by combining hexylnorbornene (39.3 mmol),triethoxysilylnorbornene (2.0 mmol), 0.08 g Irganox® 1076, and(allyl)palladium(tricyclohexylphosphine)(triflate) (3.3×10⁻⁶ ml). A 6 wt% blend was prepared by dissolving 0.75 g of a 95:5butylnorbornene:triethoxysilylnorbornene copolymer (Mw=205,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (4.6 mg, 5.3×10⁻⁶ ml) intriethoxysilylnorbornene (2.0 mmol) followed by addition ofhexylnorbornene (39.3 mmol), and 0.08 g Irganox® 1076. A 6 wt % blendwas prepared by dissolving 0.75 g of a 95:5butylnorbornene:triethoxysilylnorbornene copolymer (Mw=205,000) intocomponent B. 6 ml of viscous component A and 6 ml of viscous component Bwere separately drawn into individual glass syringes, and combined. Thecombined solution was cast onto 7″×9″ area of glass. The mixture washeated at 65° C. for 30 minutes, and cured at 180° C. for 1 hour leavingan optically transparent, odorless thin film. No regions of phaseseparation were observed.

EXAMPLE 266

Component A was prepared by combining hexylnorbornene (28 mmol),triethoxysilylnorbornene (1.5 mmol), and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (1.7×10⁻⁶ml). A 6 wt % blend was prepared by dissolving 0.33 g of a 80:20hexylnorbornene:triethoxysilylnorbornene copolymer (Mw=170,000) intocomponent A. Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (3.0 mg, 3.4×10³¹ ⁶ ml) intriethoxysilylnorbornene (1.5 mmol) followed by addition ofhexylnorbornene (28 mmol). A 6 wt % blend was prepared by dissolving0.33 g of a 80:20 hexylnorbornene:triethoxysilylnorbornene copolymer(Mw=170,000) into component B. 6 ml of viscous component A and 6 ml ofviscous component B were separately drawn into individual glasssyringes, and combined. The combined solution was cast onto a 7″×9″area. The mixture was heated at 65° C. for 30 minutes and cured at 180°C. for 1 hour leaving an optically transparent, odorless thin film. Noregions of phase separation were observed.

EXAMPLE 267

Component A was prepared by combining hexylnorbornene (34 mmol),5-triethoxysilylnorbornene (3.7 mmol), and(allyl)platinum(tricyclohexylphosphine) triflate (4.5×10⁻⁶ ml).Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (6.0 mg, 6.9×10⁻⁶ ml) in5-triethoxysilylnorbornene (3.7 mmol) followed by addition ofhexylnorbornene (34 mmol). Components A and B were combined via syringe,heated while under nitrogen at 80° C. for 8 hours until a solid slightlyopaque puck was obtained.

EXAMPLE 268

Component A was prepared by combining hexylnorbornene (34 mmol) and(methallyl) nickel (tricyclohexylphosphine) triflate (5.5×10⁻⁵ ml).Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)boratee2.5 Et₂O (60.0 mg, 6.9×10⁻⁵ ml) in 150μl dichloromethane followed by addition of hexylnorbornene (34 mmol).Components A and B were combined via syringe and while under nitrogen at80° C. for 8 hours until a solid, light orange puck was obtained.

EXAMPLE 269

Component A was prepared by combining hexylnorbornene (34 mmol) and(allyl)platinum (tricyclohexylphosphine) triflate (3.8×10⁻⁵ ml).Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (60.0 mg, 6.9×10⁻⁵ ml) in 150μl dichloromethane followed by addition of hexylnorbornene (34 mmol).Components A and B were combined via syringe, heated while undernitrogen at 80° C. for 8 hours until a solid slightly opaque puck wasobtained.

EXAMPLE 270

Perfluorohexylnorbornene monomer (3 g, 7.3 mmol) was combined withlithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (3.0 mg, 0.0034mmol). The mixture was sonicated in order to dissolve the solid in themonomer. The catalyst,(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.03 ml of a0.0128 M solution in methylene chloride) was added to the mixture. Themixture was then poured onto a mold placed on a hot plate maintained at65° C. The solution was heated at 65 ° C. for 15 minutes, then at 90° C.for 15 minutes, then at 130 ° C. for 15 minutes, and finally at 180 ° C.for 30 minutes. A clear, transparent film was obtained, which wasinsoluble in organic solvents and perfluorinated solvents.

EXAMPLE 271

Hexylnorbornene (1 g, 5.6 mmol) and 5-(perfluorobutyl) norbornene (1.17g, 3.7 mmol) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.6 mg, 0.0018 mmol). Tothis mixture, the catalyst(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.03 ml of a0.0128 M solution in methylene chloride) was added. The mixture wasallowed to increase in viscosity and then poured onto a glass plate andspread out using a doctor-blade. The glass plate was placed in an ovenat 65° C. for 30 minutes and then under vacuum at 100° C. for 60minutes. An optically clear film was obtained.

EXAMPLE 272 Synthesis of Deuterated Cyclopentadiene.

Method 1: This method is a modification of a procedure described in theliterature: Renaud, R. N., Stephens, J. C J. Label. Compounds 1967, 3(suppl. No. 1), 416-419.

A high pressure autoclave equipped with an agitator, was charged withfreshly cracked cyclopentadiene (46.8 g, 0.71 mol). This was quicklyfollowed by a solution of sodium carbonate (25 g, 0.24 mol) in deuteriumoxide (100 g). The temperature is increased to 160° C. and maintained atthat temperature for 40 hours. After the reactor had cooled to roomtemperature, the resulting emulsion was removed from the reactor andallowed to separate. The organic layer was then separated from theaqueous layer. It is cracked to obtain the deuterated cyclopentadiene.

Method 2: This method is modification of the procedure described in theliterature: Lambert, J. B., Finzel, R. B. J. Am. Chem. Soc. 1983, 105,1954-1958.

To a mixture of freshly cracked cyclopentadiene (50 g) and dimethylsulfoxide (40 ml), maintained at 0° C., was added a NaOD/D₂O mixture.The NaOD/D₂O mixture was obtained by adding sodium metal (10 g) todeuterium oxide (60 ml) while maintaining the temperature below 10° C.The mixture was allowed to stir vigorously for 1 hour. The top layer,which contained the cyclopentadiene was then separated and stirred witha fresh mixture of NaOD/D₂O. This process was repeated a total of 4times. The final product (35 ml) was then distilled.

EXAMPLE 273

Deuterocyclopentadiene (10 g, 0.14 mol) was combined with 1H, 1H,2H-perfluoro-1-octene (50 g, 0.15 mol). The mixture was allowed to stirat 0° C. for 2 hours and was heated to reflux for 2 hours. After thesolution had cooled down, the product was obtained by vacuumdistillation. Obtained pure product,1,2,3,4,7,7-hexadeutero-5-(perfluorobutyl) norbornene (30 g, 52% yield).

EXAMPLE 274

Hexylnorbornene (2 g, 11.2 mmol) and1,2,3,4,7,7-hexadeutero-5-(perfluorobutyl)norbornene (3.6 g, 11.2 mmol)were combined with lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O(3.9 g, 0.0044 mmol). To this mixture, the catalyst(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.07 ml of a0.0128 M solution in methylene chloride) was added. The solution wasallowed to increase in viscosity and then poured onto a glass plate andspread out using a doctor-blade. The glass plate was placed in an ovenat 65° C. for 30 minutes and under vacuum at 100° C. for 60 minutes. Anoptically clear film was obtained.

EXAMPLE 275

Hexylnorbornene (6 g, 34 mmol), triethoxysilylnorbornene (0.66 g, 2.6mmol), tetracylcododecane (2.05 g, 12.8 mmol) and tetracyclododecadiene(0.41 g, 2.6 mmol) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (3.0 mg, 0.0034 mmol). Tothis mixture, the catalyst(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.05 ml of a0.0128 M solution in methylene chloride) was added. The mixture wasfiltered through a 0.2 micron PTFE syringe filter into a test tube. Thiswas then placed in an oil bath maintained at 90° C. for 60 minutes. Thetemperature was then increased to 200° C. and the mixture was maintainedat this temperature for 90 minutes. An optically clear rod of thepolymer was obtained by carefully breaking the test tube.

EXAMPLE 276

Hexylnorbornene (6 g, 34 mmol), triethoxysilylnorbornene (0.62 g, 2.4mmol) and tetracylcododecane (1.9 g, 11.8 mmol) were combined withlithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (3.0 mg, 0.0034mmol). To this mixture, the catalyst(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.05 ml of a0.0128 M solution in methylene chloride) was added. The mixture wasfiltered through a 0.2 micron PTFE syringe filter into a test tube. Thiswas then placed in an oil bath maintained at 90° C. for 60 minutes. Thetemperature was then increased to 200° C. and the mixture was maintainedat this temperature for 90 minutes. A clear rod of the polymer wasobtained by carefully breaking the test tube.

Hexylnorbornene (5 g, 28.1 mmol), triethoxysilylnorbornene (0.39 g, 1.5mmol) and benzylether of 5-norbornene methanol (0.35 g, 1.6 mmol) werecombined with lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.3mg, 0.0026 mmol). To this mixture, the catalyst(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.05 ml of a0.0128 M solution in methylene chloride) was added. The solution wasfiltered through a 0.2 micron PTFE syringe filter into a test tube. Thiswas then placed in an oil bath maintained at 90° C. for 60 minutes. Thetemperature was then increased to 200° C. and the solution wasmaintained at this temperature for 90 minutes. An optically clear rod ofthe polymer was obtained by carefully breaking the test tube.

EXAMPLE 277

Hexylnorbornene (6 g, 33.7 mmol), triethoxysilylnorbornene (1.1 g, 4.3mmol), benzylether of 5-norbornene methanol (0.45 g, 2.1 mmol) andtetracyclodecadiene (0.33 g, 2.1 mmol) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.8 mg, 0.0021 mmol). Tothis mixture, the catalyst(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.07 ml of a0.0128 M solution in methylene chloride) was added. The mixture wasfiltered through a 0.2 micron PTFE syringe filter into a test tube. Thiswas then placed in an oil bath maintained at 90° C. for 60 minutes. Thetemperature was then increased to 180° C. and the mixture was maintainedat this temperature for 120 minutes. An optically clear rod of thepolymer was obtained by carefully breaking the test tube.

2-methyl propylnorbornene (7.0 g, 46 mmol), triethoxysilylnorbornene(1.33 g, 5.2 mmol) and Irganox® 1076 (0.8 g, 1 wt %) (Ciba Geigy) werecombined with lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (5.6mg, 0.0063 mmol). To this mixture, the catalyst(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.1 ml of a0.0128 M solution in methylene chloride) was added. This mixture wasfiltered through a 0.2 micron PTFE filter and poured onto a mold on aglass plate and placed in an oven maintained at 65° C. for 30 minutes.The glass plate was then heated at 180° C. for 60 minutes. Obtained anoptically clear film.

EXAMPLE 278

Hexylnorbornene (4.7 g, 26 mmol), 2-methyl propylnorbornene (4.0 g, 26mmol), triethoxysilylnorbornene (1.50 g, 6.0 mmol) and Irganox® 1076(1.2 g, 1 wt %) (Ciba-Geigy) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (6.3 mg, 0.0072 mmol). Tothis mixture, the catalyst(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.11 ml of a0.0128 M solution in methylene chloride) was added. This mixture wasfiltered through a 0.2 micron PTFE filter and poured onto a mold on aglass plate and placed in an oven maintained at 65° C. for 30 minutes.

The glass plate was then heated at 180° C. for 60 minutes. An opticallyclear film was obtained.

EXAMPLE 279

Hexylnorbornene (12.0 g, 67.4 mmol), triethoxysilylnorbornene (2.05 g,8.0 mmol), norbornadiene dimer (0.74 g, 4.0 mmol) were combined withlithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (5.5 mg, 0.0063mmol). To this mixture was added an antioxidant, Irganox® 1076 (0.15 g)(Ciba Geigy). The catalyst,(allyl)palladium(tricylcohexylphosphine)trifluoroacetate (0.25 ml of a0.0128 M solution in methylene chloride) was added to the mixture. Themixture was then poured onto a mold on a glass plate and heated in anoven at 65° C. for 30 minutes. It was then heated at 180° C. for 60minutes. The film obtained was optically clear.

EXAMPLE 280

Component A was prepared by combining hexylnorbornene (28.1 mmol)triethoxysilylnorbornene (3.3 mmol), and(allyl)palladium(tricyclohexylphosphine)(trifluoroacetate) (2.5×10⁻⁶ml). Component B was prepared by dissolving lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (5×10⁻⁶ ml) intriethoxysilylnorbornene (3.3 mmol) followed by addition ofhexylnorbornene (28.1 mmol). 6 ml of component A and 6 ml of component Bwere separately drawn into individual glass syringes, and combined afterfiltration through a 0.2 μm filter disk. The combined solution was castonto 7″×9″ area of glass. The cast solution was heated at 65° C. for 30minutes in an air recirculating oven. This film was then cut into 12pieces and then cured at the following temperatures (160, 170 and 180°C. ) in an air recirculating oven and removed at 15 minute intervals toform optically transparent thin films. These films were then analyzedusing thermogravimetric analysis (nitrogen purge, analysis heating rateis

% loss @ % loss @ % loss @ Temperature (C.) Time (min) 250 300 320 A 18015 1.67 2.36 2.78 B 180 30 0.84 1.66 2.11 C 180 45 0.68 1.35 1.79 D 18060 0.65 1.35 1.79 E 170 15 1.71 2.45 2.93 F 170 30 0.86 1.65 2.09 G 17045 0.27 1.23 1.63 H 170 60 0.47 1.23 1.68 I 160 15 1.83 2.79 3.19 J 16030 0.61 1.70 2.04 K 160 45 0.37 1.37 1.76 L 160 60 0.34 1.16 1.61

EXAMPLE 281

Hexylnorbornene (5 g, 28.1 mmol), triethoxysilyl norbornene (0.39 g, 1.5mmol) and benzylether of 5-norbornene methanol (0.35 g, 1.6 mmol) werecombined with lithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (2.3mg, 0.0026 mmol). To this mixture, the catalyst(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.05 ml of a0.0128 M solution in methylene chloride) was added. The mixture wasfiltered through a 0.2 micron PTFE syringe filter into a test tube. Thiswas then placed in an oil bath maintained at 90° C. for 60 minutes. Thetemperature was then increased to 200° C. and the mixture was maintainedat this temperature for 90 minutes. An optically clear rod of thepolymer was obtained by carefully breaking the test tube.

EXAMPLE 282

Hexylnorbornene (6 g, 33.7 mmol), triethoxysilyl norbornene (1.1 g, 4.3mmol), benzylether of 5-norbornene methanol (0.45 g, 2.1 mmol) andtetracyclodecadiene (0.33 g, 2.1 mmol) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.8 mg, 0.0021 mmol). Tothis mixture, the catalyst(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.07 ml of a0.0128 M solution in methylene chloride) was added. The mixture wasfiltered through a 0.2 micron PTFE syringe filter into a test tube. Thiswas then placed in an oil bath maintained at 90° C. for 60 minutes. Thetemperature was then increased to 180° C. and the mixture was maintainedat this temperature for 120 minutes. An optically clear rod of thepolymer was obtained by carefully breaking the test tube.

EXAMPLE 283

Hexylnorbornene (5 g, 28.1 mmol.) and triethoxysilylnorbornene (0.38 g,1.5 mmol.) were combined with lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.001 mmol). To thismixture, the catalyst(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.05 ml of a0.0128 M solution in methylene chloride) was added. The mixture wasfiltered through a 0.2 micron PTFE syringe filter into a test tube. Thiswas then placed in an oil bath maintained at 90° C. for 60 minutes. Thetemperature was then increased to 200° C. and the mixture was maintainedat this temperature for 90 minutes. An optically clear rod of thepolymer was obtained by carefully breaking the test tube.

EXAMPLE 284

Hexylnorbornene (5 g, 28.1 mmol.), triethoxysilylnorbornene (0.85 g, 3.3mmol.) and tetracyclododecadiene (0.26 g, 1.64 mmol.) were combined withlithium tetrakis(pentafluorophenyl)borate·2.5 Et₂O (1.4 mg, 0.001 mmol).To this mixture, the catalyst(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (0.05 ml of a0.0128 M solution in methylene chloride) was added. The mixture wasfiltered through a 0.2 micron PTFE syringe filter into a test tube. Thiswas then placed in an oil bath maintained at 90° C. for 60 minutes. Thetemperature was then increased to 200° C. and the mixture was maintainedat this temperature for 90 minutes. An optically clear rod of thepolymer was obtained by carefully breaking the test tube.

EXAMPLE 285

Palladium(II) trifluoroacetate (0.50 g, 1.5 mmol), allyltributyltin(0.50 g, 1.5 mmol), and tricyclohexylphosphine (0.42 g, 1.5 mmol) weremixed in toluene under nitrogen. After about an 1-½ hours, some blackprecipitate formed. The mixture was filtered though Celite®. Theresulting orange solution was stored in the freezer overnight. The nextday, the solution was refiltered through Celite®. The solvent wasremoved in vacuo from the filtrate. The resulting solid was washed withpentane. A colorless solid was obtained. Yield 0.39 g. ³¹p NMR (CD₂Cl₂):δ 41.6 (s) and unidentified peak at 24.2 (s, approx. 20% of the total).¹H NMR (CD₂Cl₂): δ 5.47 (m, 1H), 4.79 (t, 1H), 3.83 (d of d, 1H), 3.25(s, 1H), 2.51 (d, 1H), and peaks from 1.9 to 1.0 due totricyclohexylphosphine.

EXAMPLE 296

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of palladium(II) acetate (0.28 μmol) andtricyclohexylphosphine (0.28 μmol) in fluorobenzene. The mixture washeated to 80° C. for 10 minutes. An immobile polymer puck resulted,suggesting high conversion.

EXAMPLE 287

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of palladium(II) trifluoroacetate (0.28 μmol)and tricyclohexylphosphine (0.28 μmol) in fluorobenzene. The mixture washeated to 80° C. for 10 minutes. An immobile polymer puck resulted,suggesting high conversion.

EXAMPLE 288

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of palladium(II) acetylacetonate (0.28 μmol)and tricyclohexylphosphine (0.28 μmol) in fluorobenzene. The mixture washeated to 80° C. for 10 minutes. An immobile polymer puck resulted,suggesting high conversion.

EXAMPLE 289

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of palladium(0) bis(tricyclohexylphosphine)(0.28 μmol) in toluene. The mixture was heated to 80° C. overnight. Animmobile polymer puck resulted, suggesting high conversion.

EXAMPLE 290

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of bis(tricyclohexylphosphine)palladiumdichloride (0.28 μmol) in methylene chloride. The mixture was heated to65° C. for 18 hours. An immobile polymer puck resulted, suggesting highconversion.

EXAMPLE 291

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of bis(triethylphosphine)palladium dichloride(0.28 μmol) in methylene chloride. The mixture was heated to 65° C. for18 hours. An immobile polymer puck resulted, suggesting high conversion.

EXAMPLE 292

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of bis(triphenylphosphine)palladium dichloride(0.28 μmol) in methylene chloride. The mixture was heated to 65° C. for18 hours. An immobile polymer puck resulted, suggesting high conversion.

EXAMPLE 293

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50AL of a 5.5 mMol solution of bis(tri-o-tolylphosphine)palladiumdichloride (0.28 μmol) in methylene chloride. The mixture was heated to65° C. for 18 hours. An immobile polymer puck resulted, suggesting highconversion.

EXAMPLE 294

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of bis(tributylphosphine)nickel dibromide(0.28 μmol) in methylene chloride. The mixture was heated to 65° C. for18 hours. An immobile polymer puck resulted, suggesting high conversion.

EXAMPLE 295

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with toluene. To this mixture was added 50μL of a 5.5 mMol solution of bis(triphenyllphosphine)nickel dibromide(0.28 μmol) in methylene chloride. The mixture was heated to 65° C. for18 hours. A viscous solution resulted. The solution was diluted withtoluene and poured into an excess of acetone to precipitate the polymer.The polymer was filtered, and dried under vacuum at 65° C. Yield 4 g(80%).

EXAMPLE 296.

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 mL with toluene. To this mixture was added 50μL of a 5.5 mMol solution of nickel bis(cyclooctadiene) (0.28 μmol) inmethylene chloride and 2-(diphenylphosphino)benzoic acid (0.28 μmol).The mixture was heated to 65° C. for 18 hours. The solution was dilutedwith toluene and poured into an excess of acetone to precipitate thepolymer. The polymer was filtered, and dried under vacuum at 65° C.Yield 1 g (20%).

EXAMPLE 297

Palladium(II) acetate (0.0056 g) and tricyclohexylphosphine (0.0088 g)were dissolved in Hexylnorbornene (50 g, 0.28 mol) andtriethoxysilylnorbornene (8.0 g, 0.031 mol). Lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.065 g) was dissolved inhexylnorbornene (50 g, 0.28 mol) and triethoxysilylnorbornene (8.0 g,0.031 mol). Equal volumes of each solution were mixed together. Thesolution was allowed to thicken and was then poured onto a glass plate.The plate was placed into an oven at 65° C. for 10 min, then heated to160° C. for one hour. A transparent film resulted. The film exhibited2.1% weight loss at 320° C. by TGA (10° C./min). The film exhibited aglass transition temperature of 278° C. as determined by the tan 6 peakin its DMA trace.

EXAMPLE 298

Palladium(II) acetate (0.0056 g) was dissolved in hexylnorbornene (50 g,0.28 mol) and triethoxysilylnorbornene (8.0 g, 0.031 mol). Lithiumtetrakis(pentafluorophenyl)borate·2.5 Et₂O (0.065 g) andtricyclohexylphosphine (0.0088 g) were dissolved in hexylnorbornene (50g, 0.28 mol) and triethoxysilylnorbornene (8.0 g, 0.031 mol). Equalvolumes of each solution were mixed together. The solution was allowedto thicken and was then poured onto a glass plate. The plate was placedinto an oven at 65° C. for 10 min, then heated to 160° C. for one hour.A transparent film resulted. The film exhibited 3.3% weight loss at 320°C. by TGA (10° C. /min). The film exhibited a glass transitiontemperature of 274° C. as determined by the tan 8 peak in its DMA trace.

EXAMPLE 299

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with cyclohexane. To this mixture was added50 μL of a 2.8 mMol solution of (allyl)palladiumtrifluoroacetate dimer(0.14 μmol) and tetraphenylbiphosphine (0.28 μmol) in methylenechloride. The mixture was heated to 65° C. for 18 hours. An immobilepolymer puck resulted, suggesting high conversion.

EXAMPLE 300

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with cyclohexane. To this mixture was added50 μL of a 2.8 mMol solution of (allyl)palladiumtrifluoroacetate dimer(0.14 μmol) and 1,2-bis(diphenylphosphino)propane (0.28 μmol) inmethylene chloride. The mixture was heated to 65° C. for 18 hours. Thesolution was poured into an excess of acetone. No significant amounts ofpolymer were obtained.

EXAMPLE 301

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with cyclohexane. To this mixture was added50 μL of a 2.8 mMol solution of (allyl)palladiumtrifluoroacetate dimer(0.14 μmol) and 1,2-bis(diphenylphosphino)propane (0.28 μmol) inmethylene chloride. The mixture was heated to 65° C. for 18 hours.Addition of the mixture to an excess of acetone gave no polymer.

EXAMPLE 302

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with cyclohexane. To this mixture was added50 μL of a 2.8 mMol solution of (allyl)palladiumtrifluoroacetate dimer(0.14 μmol) and (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl(0.28 μmol) in methylene chloride. The mixture was heated to 65° C. for18 hours.

An immobile polymer puck resulted, suggesting high conversion.

EXAMPLE 303

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with cyclohexane. To this mixture was added50 μL of a 2.8 mMol solution of (allyl)palladiumtrifluoroacetate dimer(0.14 μmol) and 1,2-bis(dicyclohexylphosphino)ethane (0.28 μmol) inmethylene chloride. The mixture was heated to 65° C. for 18 hours. Aviscous solution resulted. The solution was diluted with toluene andpoured into an excess of acetone to precipitate the polymer. The polymerwas filtered, and dried under vacuum at 65° C. Yield 4 g (80%).

EXAMPLE 304

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with cyclohexane. To this mixture was added50 μL of a 2.8 mMol solution of (allyl)palladiumtrifluoroacetate dimer(0.14 μmol) and 1,2-bis(diphenylphosphino)methane (0.28 μmol) inmethylene chloride. The mixture was heated to 65° C. for 18 hours. Aviscous solution resulted. The solution was diluted with toluene andpoured into an excess of acetone to precipitate the polymer. The polymerwas filtered, and dried under vacuum at 65° C. Yield 1.6 g (32%).

EXAMPLE 305

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate 2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with cyclohexane. To this mixture was added50 μL of a 2.8 mMol solution of (allyl)palladiumtrifluoroacetate dimer(0.14 μmol) and 1,2-bis(dicyclohexylphosphino)methane (0.28 μmol) inmethylene chloride. The mixture was heated to 65° C. for 18 hours. Aviscous solution resulted. The solution was diluted with toluene andpoured into an excess of acetone to precipitate the polymer. The polymerwas filtered, and dried under vacuum at 65° C. Yield 2.9 g (58%).

EXAMPLE 306

To a mixture of butylnorbornene (5.0 g, 33 mmol) was added lithiumtetrakis(penta-fluorophenyl)borate·2.5 Et₂O (1.2 mg, 0.0014 mmol). Thismixture was diluted to 16 ml with cyclohexane. To this mixture was added50 μL of a 2.8 mMol solution of (allyl)palladiumrifluoroacetate dimer(0.14 μmol) and 1,2-bis(diphenylphosphino)ethane (0.28 μmol) inmethylene chloride. The mixture was heated to 65° C. for 18 hours. Thesolution was diluted with toluene and poured into an excess of acetoneto precipitate the polymer. The polymer was filtered, and dried undervacuum at 65° C. Yield 2.9 g (58%).

EXAMPLE 307

In a glove box, under an inert atmosphere (nitrogen),[(1,5-cyclooctadiene)Pd(Me)(Cl)] (3.02×10⁻⁷ mol) was placed into a 25 mlround bottom flask and dissolved in ca. 5 ml CH₂Cl₂. To this was added 1equivalent of PPh₃. Then, 1 equivalent of sodium[tetrakis(bis(3,5-trifluoromethyl)phenyl)borate] was added to thesolution. Norbornene (0.106 mol) was added, and the mixture was gentlyswirled. The flask was placed onto a stir plate. Polymerization wascomplete (the mixture solidified) within 2 minutes. Polymer product wasobtained by diluting in methanol, then decanting off liquid and dryingunder reduced pressure at room temperature. Approximately 100% yield wasobtained (1.05×10⁶ turnovers/hr). Molecular weight was not determineddue to the insolubility of the product.

EXAMPLE 308

In a glove box, under an inert atmosphere (nitrogen),[(1,5-cyclooctadiene)Pd(Me)(Cl)] (1.13×10⁻⁷ mol) was placed into a 25 mlround bottom flask and dissolved in ca. 5 mL CH₂Cl₂. To this was added 1equivalent of PPh₃. Then, 1 equivalent of sodium[tetrakis(bis(3,5-trifluoromethyl)phenyl)borate] was added to thesolution. Dicyclopentadiene (0.106 mol) was added, and the mixture wasgently swirled. The flask was placed onto a stir plate. Polymerizationwas complete (the mixture solidified) within 5 minutes. Polymer productwas obtained by diluting in methanol, then decanting off liquid anddrying under reduced pressure at room temperature. Approximately 100%yield was obtained. Molecular weight was not determined due to theinsolubility of the product.

What is claimed is:
 1. A process for preparing a polymer containingpolycyclic repeating units comprising contacting at least onepolycycloolefin monomer with a high activity Group 10 transition metalcatalyst complex of the formula:[(R′)_(z)M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d) to obtain a polymer productthat contains 100 ppm or less of residual Group 10 transition metalprior to purification, wherein [(R′)_(z)M(L′)_(x)(L″)_(y)] is a cationcomplex where M represents a Group 10 transition metal; R′ represents ananionic hydrocarbyl containing ligand; L′ represents a Group neutralelectron donor ligand; L″ represents a labile neutral electron donorligand; x is 1 or 2; and y is 0, 1, 2, or 3; and z is 0 or 1, whereinthe sum of x, y, and z is 4; [WCA] represents a weakly coordinatingcounteranion complex; and b and d are numbers representing the number oftimes the cation complex and weakly coordinating counteranion complexare taken to balance the electronic charge on the overall catalystcomplex.
 2. The process of claim 1 wherein said polycycloolefin isselected from a monomer(s) of the formula:

wherein “a” represents a single or double bond, m is an integer from 0to 5, and when “a” is a double bond one of R¹, R² and one of R³, R⁴ isnot present; R¹ to R⁴ independently represent hydrogen, substituted andunsubstituted linear and branched C₁-C₁₀ alkyl, linear and branchedC₁-C₁₀ haloalkyl, substituted and unsubstituted linear and branchedC₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ haloalkenyl, substituted andunsubstituted linear and branched C₂-C₁₀ alkynyl, substituted andunsubstituted C₄-C₁₂ cycloalkyl, substituted and unsubstituted C₄-C₁₂halocycloalkyl, substituted and unsubstituted C₄-C₁₂ cycloalkenyl,substituted and unsubstituted C₄-C₁₂ halocycloalkenyl, substituted andunsubstituted C₆-C₁₂ aryl, substituted and unsubstituted C₆-C₁₂ haloaryland substituted and unsubstituted C₇-C₂₄ aralkyl, R¹ and R² or R³ and R⁴can be taken together to represent a C₁-C₁₀ alkylidenyl group,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵,—(CH₂)_(n)—OC(O)R⁵, —(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵,—(CH₂)_(n)SiR⁵, —(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)C(O)OR⁶, and the group:

wherein n independently represents an integer from 0 to 10 and R⁵independently represents hydrogen, linear and branched C₁-C₁₀ alkyl,linear and branched, C₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ alkynyl,C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, and C₇-C₂₄ aralkyl; R⁶ represents aradical selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃,—CH(R⁷)OC(CH₃)₃, dicyclopropylmethyl, dimethylcyclopropylmethyl, or thefollowing cyclic groups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup; R¹ and R⁴ together with the two ring carbon atoms to which theyare attached can represent a substituted or unsubstituted cycloaliphaticgroup containing 4 to 30 ring carbon atoms, a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms andcombinations thereof; R¹ and R⁴ can be taken together to form thedivalent bridging group, —C(O)—Q—(O)C—, which when taken together withthe two ring carbon atoms to which they are attached form a pentacyclicring, wherein Q represents an oxygen atom or the group N(R⁸), wherein R⁸is selected from hydrogen, halogen, linear and branched C₁-C₁₀ alkyl, orC₆-C₁₈ aryl.
 3. The process of claim 1 wherein said Group 10 transitionmetal M is selected from palladium, platinum or nickel, and said Group15 neutral electron donor ligand L is selected from amines, pyridines,arsines, stibines or organophosphorus containing compounds.
 4. Theprocess of claim 3 wherein said organophosphorus containing ligand isselected from a compound of the formula:  P(R⁷′)_(g)[X′(R⁷′)_(h)]_(3−g)wherein X′ is oxygen, sulfur, nitrogen, or silicon; g is 0, 1, 2, or 3;h is 1, 2, or 3, with the proviso that when X′ is a silicon atom, h is3, when X′ is an oxygen or sulfur atom h is 1, and when X′ is a nitrogenatom, h is 2; R⁷′ is independently selected from hydrogen, linear andbranched C₁-C₁₀ alkyl, C₅-C₁₀ cycloalkyl, linear and branched C₁-C₁₀alkoxy, allyl, linear and branched C₂-C₁₀ alkenyl, C₆-C₁₂ aryl, C₆-C₁₂aryloxy, C₆-C₁₂ arylsulfides, C₇-C₁₈ aralkyl, cyclic ethers andthioethers, tri(linear and branched C₁-C₁₀ alkyl)silyl, tri(C₆-C₁₂aryl)silyl, tri(linear and branched C₁-C₁₀ alkoxy)silyl,triaryloxysilyl, tri(linear and branched C₁-C₁₀ alkyl)siloxy, ortri(C₆-C₁₂ aryl)siloxy, wherein each of the foregoing substituents canbe optionally substituted with linear or branched C₁-C₅ alkyl, linear orbranched C₁-C₅ haloalkyl, C₁-C₅ alkoxy, halogen, and combinationsthereof; when g is 0 and X′ is oxygen, any two or 3 of R⁷′ can be takentogether with the oxygen atoms to which they are attached to form acyclic moiety; when g is 3 any two of R⁷′ can be taken together with thephosphorus atom to which they are attached to represent a phosphacycleof the formula:

wherein R⁷′ is as previously defined and h′ is an integer from 4 to 11.5. The process of claim 3 wherein said organophosphorus containingligand is a bidentate phosphine selected from the formulae:

wherein R7′ is as defined and i is 0, 1, 2, or
 3. 6. The process ofclaim 4 wherein g is 3 and R⁷′ is independently selected from the groupconsisting of hydrogen, linear and branched C₁-C₁₀ alkyl, C₅-C₁₀cycloalkyl, linear and branched C₁-C₁₀ alkoxy, allyl, linear andbranched C₂-C₁₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ aryloxy.
 7. The processof claim 1 wherein the weakly coordinating counteranion complex isselected from the group consisting of borates, aluminates, boratobenzeneanions, carborane anions, and halocarborane anions.
 8. The process ofclaim 7 wherein the weakly coordinating anion is a borate or aluminateof the formula: ti [M′(R²⁴′)(R²⁵′)(R²⁶′)(R²⁷′)] wherein in Formula M′ isboron or aluminum and R²⁴′, R²⁵′, R²⁶′, and R²⁷′ independently representfluorine, linear and branched C₁-C₁₀ alkyl, linear and branched C₁-C₁₀alkoxy, linear and branched C₃-C₅ haloalkenyl, linear and branchedC₃-C₁₂ trialkylsiloxy, C₁₈-C₃₆ triarylsiloxy, substituted andunsubstituted C₆-C₃₀ aryl, and substituted and unsubstituted C₆-C₃₀aryloxy groups wherein R²⁴′ to R²⁷′ can not simultaneously representalkoxy or aryloxy groups.
 9. The process of claim 8 wherein saidsubstituted aryl and aryloxy groups are be monosubstituted ormultisubstituted and said substituents are independently selected fromlinear and branched C₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl,linear and branched C₁-C₅ alkoxy, linear and branched C₁-C₅ haloalkoxy,linear and branched C₁-C₁₂ trialkylsilyl, C₆-C₁₈ triarylsilyl, orhalogen selected from chlorine, bromine, or fluorine.
 10. The process ofclaim 8 wherein said borate is selected from the group consisting oftetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-i-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,(triphenylsiloxy)tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate,tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate.11. The process of claim 8 wherein said aluminate is selected from thegroup consisting of tetrakis(pentafluorophenyl)aluminate,tris(perfluorobiphenyl)fluoroaluminate,(octyloxy)tris(pentafluorophenyl)aluminate,tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, andmethyltris(pentafluorophenyl)aluminate.
 12. The process of claim 7wherein the weakly coordinating anion is a borate or aluminate of theformula: [M′(OR²⁸′)(OR²⁹′)(OR³⁰′)(OR³¹′)] M′ is boron or aluminum, R²⁸′,R²⁹′, R³⁰′, and R³¹′ independently represent linear and branched C₁-C₁₀alkyl, linear and branched C₁-C₁₀ haloalkyl, C₂-C₁₀ haloalkenyl,substituted and unsubstituted C₆-C₃₀ aryl, and substituted andunsubstituted C₇-C₃₀ aralkyl groups, subject to the proviso that atleast three of R²⁸′ to R³¹′ must contain a halogen containingsubstituent; OR²⁸′ and OR²⁹′ can be taken together to form a chelatingsubstituent represented by —O—R³²′—O—, wherein the oxygen atoms arebonded to M′ and R³²′ is a divalent radical selected from substitutedand unsubstituted C₆-C₃₀ aryl and substituted and unsubstituted C₇-C₃₀aralkyl.
 13. The process of claim 12 wherein said substituted aryl andaralkyl groups are monosubstituted or multisubstituted, and saidsubstituents are independently selected from linear and branched C₁-C₅alkyl, linear and branched C₁-C₅ haloalkyl, linear and branched C₁-C₅alkoxy, linear and branched C₁-C₁₀ haloalkoxy, or halogen selected fromchlorine, bromine, or fluorine, fluorine.
 14. The process of claim 12wherein said borate is selected from the group consisting of[B(OC(CF₃)₃)₄]⁻, [B(OC(CF₃)₂(CH₃))₄]⁻, [B(OC(CF₃)₂H)₄]⁻,[B(OC(CF₃)(CH₃)H)₄]⁻, and [B(OCH₂(CF₃)₂)₄]⁻.
 15. The process of claim 12wherein said aluminate is selected from the group consisting of,[Al(OC(CF₃)₂Ph)₄]⁻, [Al(OC(CF₃)₂C₆H₄CH₃)₄]⁻, [Al(OC(CF₃)₃)₄]⁻,[Al(OC(CF₃)(CH₃)H)₄]⁻, [Al(OC(CF₃)₂H)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]⁻,[Al(OC(CF₃)₂C₆H₄-4-t-butyl)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄, ]⁻,[Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,]⁻,[Al(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄]⁻,[Al(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄]⁻, [Al(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄]⁻, and[Al(OC(C(CF₃)₂C₆F₅)₄]⁻.
 16. A process for preparing a polymer containingpolycyclic repeating units comprising contacting at least onepolycycloolefin monomer with a high activity Group 10 transition metalcatalyst complex of the formula:[(R′)_(z)M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d) to obtain a polymer productthat contains 100 ppm or less of residual Group 10 transition metalprior to purification, wherein [(R′)_(z)M(L′)_(x)(L″)_(y)] is a cationcomplex where M represents a Group 10 transition metal; R′ represents aligand selected from the group consisting of R″C(O)O, R″C(O)CHC(O)R″,R″C(O)S, R″C(S)O, R″O, R″₂N, and R″₂P, wherein R″ represents hydrogen,linear and branched C₁-C₂₀ alkyl, C₅-C₁₀ cycloalkyl, linear and branchedC₂-C₂₀ alkenyl, C₆-C₁₅ cycloalkenyl, allylic ligands or canonical formsthereof, C₆-C₃₀ aryl, C₆-C₃₀ heteroatom containing aryl, and C₇-C₃₀aralkyl, wherein each of the foregoing radicals are optionallysubstituted with a substituent selected from the group consisting oflinear or branched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl,linear or branched C₂-C₅ alkenyl C₂-C₅ haloalkenyl, halogen, sulfur,oxygen, nitrogen, phosphorus, and phenyl, wherein said phenyl group isoptionally substituted with linear or branched C₁-C₅ alkyl, linear orbranched C₁-C₅ haloalkyl, and halogen; L′ represents a Group 15 neutralelectron donor ligand; L″ represents a labile neutral electron donorligand; x is 1 or 2; and y is 0, 1, 2, or 3; and z is 0 or 1, whereinthe sum of x, y, and z is 4; [WCA] represents a weakly coordinatingcounteranion complex; and b and d are numbers representing the number oftimes the cation complex and weakly coordinating counteranion complexare taken to balance the electronic charge on the overall catalystcomplex.
 17. The process of claim 16 wherein said polycycloolefin isselected from a monomer(s) of the formula:

wherein “a” represents a single or double bond, m is an integer from 0to 5, and when “a” is a double bond one of R¹, R² and one of R³, R⁴ isnot present; R¹ to R⁴ independently represent hydrogen, substituted andunsubstituted linear and branched C₁-C₁₀ alkyl, linear and branchedC₁-C₁₀ haloalkyl, substituted and unsubstituted linear and branchedC₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ haloalkenyl, substituted andunsubstituted linear and branched C₂-C₁₀ alkynyl, substituted andunsubstituted C₄-C₁₂ cycloalkyl, substituted and unsubstituted C₄-C₁₂halocycloalkyl, substituted and unsubstituted C₄-C₁₂ cycloalkenyl,substituted and unsubstituted C₄-C₁₂ halocycloalkenyl, substituted andunsubstituted C₆-C₁₂ aryl, substituted and unsubstituted C₆-C₁₂ haloaryland substituted and unsubstituted C₇-C₂₄ aralkyl, R¹ and R² or R³ and R⁴can be taken together to represent a C₁-C₁₀ alkylidenyl group,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵,—(CH₂)_(n)—OC(O)R⁵, —(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵,—(CH₂)_(n)SiR⁵, —(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)C(O)OR⁶, and the group:

wherein n independently represents an integer from 0 to 10 and R⁵independently represents hydrogen, linear and branched C₁-C₁₀ alkyl,linear and branched, C₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ alkynyl,C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, and C₇-C₂₄ aralkyl; R⁶ represents aradical selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃,—CH(R⁷)OC(CH₃)₃, dicyclopropylmethyl, dimethylcyclopropylmethyl, or thefollowing cyclic groups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup; R¹ and R⁴ together with the two ring carbon atoms to which theyare attached can represent a substituted or unsubstituted cycloaliphaticgroup containing 4 to 30 ring carbon atoms, a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms andcombinations thereof; R¹ and R⁴ can be taken together to form thedivalent bridging group, —C(O)—Q—(O)C—, which when taken together withthe two ring carbon atoms to which they are attached form a pentacyclicring, wherein Q represents an oxygen atom or the group N(R⁸), wherein R⁸is selected from hydrogen, halogen, linear and branched C₁-C₁₀ alkyl, orC₆-C₁₈ aryl.
 18. The process of claim 16 wherein said Group 10transition metal M is selected from palladium, platinum or nickel, andsaid Group neutral electron donor ligand L is selected from amines,pyridines, arsines, stibines or organophosphorus containing ligands. 19.The process of claim 18 wherein said organophosphorus containing ligandis selected from a compound of the formula:P(R⁷′)_(g)[X′(R⁷′)_(h)]_(3−g) wherein X′ is oxygen, sulfur, nitrogen, orsilicon; g is 0, 1, 2, or 3; h is 1, 2, or 3, with the proviso that whenX′ is a silicon atom, h is 3, when X′ is an oxygen or sulfur atom h is1, and when X′ is a nitrogen atom, h is 2; R⁷′ is independently selectedfrom hydrogen, linear and branched C₁-C₁₀ alkyl, C₅-C₁₀ cycloalkyl,linear and branched C₁-C₁₀ alkoxy, allyl, linear and branched C₂-C₁₀alkenyl, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₆-C₁₂ arylsulfides, C₇-C₁₈aralkyl, cyclic ethers and thioethers, tri(linear and branched C₁-C₁₀alkyl)silyl, tri(C₆-C₁₂ aryl)silyl, tri(linear and branched C₁-C₁₀alkoxy)silyl, triaryloxysilyl, tri(linear and branched C₁-C₁₀alkyl)siloxy, and tri(C₆-C₁₂ aryl)siloxy, wherein each of the foregoingsubstituents can be optionally substituted with linear or branched C₁-C₅alkyl, linear or branched C₁-C₅ haloalkyl, C₁-C₅ alkoxy, halogen, orcombinations thereof, when g is 0 and X′ is oxygen, any two or 3 of R⁷′can be taken together with the oxygen atoms to which they are attachedto form a cyclic moiety; when g is 3 any two of R⁷ can be taken togetherwith the phosphorus atom to which they are attached to represent aphosphacycle of the formula:

wherein R⁷′ is as previously defined and h′ is an integer from 4 to 11.20. The process of claim 18 wherein said organophosphorus containingligand is a bidentate phosphine selected from the formulae:

wherein R⁷′ is as defined and i is 0, 1, 2, or
 3. 21. The process ofclaim 19 wherein g is 3 and R⁷′ is independently selected from the groupconsisting of hydrogen, linear and branched C₁-C₁₀ alkyl, C₅-C₁₀cycloalkyl, linear and branched C₁-C₁₀ alkoxy, allyl, linear andbranched C₂-C₁₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ aryloxy.
 22. Theprocess of claim 16 wherein the weakly coordinating counteranion complexis selected from the group consisting of borates, aluminates,boratobenzene anions, carborane anions, and halocarborane anions. 23.The process of claim 22 wherein the weakly coordinating anion is aborate or aluminate of the formula: [M′(R²⁴′)(R²⁵′)(R²⁶′)(R²⁷′)] whereinin Formula M′ is boron or aluminum and R²⁴′, R²⁵′, R²⁶′, and R²⁷′independently represent fluorine, linear and branched C₁-C₁₀ alkyl,linear and branched C₁-C₁₀ alkoxy, linear and branched C₃-C₅haloalkenyl, linear and branched C₃-C₁₂ trialkylsiloxy, C₁₈-C₃₆triarylsiloxy, substituted and unsubstituted C₆-C₃₀ aryl, andsubstituted and unsubstituted C₆-C₃₀ aryloxy groups wherein R²⁴′ to R²⁷′can not simultaneously represent alkoxy or aryloxy groups.
 24. Theprocess of claim 23 wherein said substituted aryl and aryloxy groups arebe monosubstituted or multisubstituted and said substituents areindependently selected from linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, linear andbranched C₁-C₅ haloalkoxy, linear and branched C₁-C₁₂ trialkylsilyl,C₆-C₁₈ triarylsilyl, or halogen selected from chlorine, bromine, orfluorine.
 25. The process of claim 23 wherein said borate is selectedfrom the group consisting of tetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-i-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,(triphenylsiloxy)tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate,tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate.26. The process of claim 23 wherein said aluminate is selected from thegroup consisting of tetrakis(pentafluorophenyl)aluminate,tris(perfluorobiphenyl)fluoroaluminate,(octyloxy)tris(pentafluorophenyl)aluminate,tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, andmethyltris(pentafluorophenyl)aluminate.
 27. The process of claim 22wherein the weakly coordinating anion is a borate or aluminate of theformula: [M′(OR^(28′))(OR²⁹′)(OR³⁰′)(OR³¹′)] M′ is boron or aluminum,R²⁸′, R²⁹′, R³⁰′, and R³¹′ independently represent linear and branchedC₁-C₁₀ alkyl, linear and branched C₁-C₁₀ haloalkyl, C₂-C₁₀ haloalkenyl,substituted and unsubstituted C₆-C₃₀ aryl, and substituted andunsubstituted C₇-C₃₀ aralkyl groups, subject to the proviso that atleast three of R²⁸′ to R³¹′ must contain a halogen containingsubstituent; OR²⁸′ and OR²⁹′ can be taken together to form a chelatingsubstituent represented by —O—R³²′—O—, wherein the oxygen atoms arebonded to M′ and R³²′ is a divalent radical selected from substitutedand unsubstituted C₆-C₃₀ aryl or substituted and unsubstituted C₇-C₃₀aralkyl.
 28. The process of claim 27 wherein said substituted aryl andaralkyl groups are monosubstituted or multisubstituted, and saidsubstituents are independently selected from linear and branched C₁-C₅alkyl, linear and branched C₁-C₅ haloalkyl, linear and branched C₁-C₅alkoxy, linear and branched C₁-C₁₀ haloalkoxy, or halogen selected fromchlorine, bromine, or fluorine.
 29. The process of claim 27 wherein saidborate is selected from the group consisting of [B(OC(CF₃)₃)₄]⁻,[B(OC(CF₃)₂(CH₃))₄]⁻, [B(OC(CF₃)₂H)₄]⁻, [B(OC(CF₃)(CH₃)H)₄]⁻, and[B(OCH₂(CF₃)₂)₄]⁻.
 30. The process of claim 27 wherein said aluminate isselected from the group consisting of, [Al(OC(CF₃)₂Ph)₄]⁻,[Al(OC(CF₃)₂C₆H₄CH₃)₄]⁻, [Al(OC(CF₃)₃)₄]⁻, [Al(OC(CF₃)(CH₃)H)₄]⁻,[Al(OC(CF₃)₂H)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]⁻,[Al(OC(CF₃)₂C₆H₄-4-t-butyl)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄,]⁻,[Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,]⁻,[Al(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄]⁻,[Al(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄]⁻, [Al(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄]⁻, and[Al(OC(CF₃)₂C₆F₅)₄]⁻.
 31. A process for preparing a polymer containingpolycyclic repeating units comprising contacting a polycycloolefinmonomer with a palladium metal complex of the formula [R′Pd(L′)_(y)A′],a WCA salt containing a Group 1 metal cation and a weakly coordinatingcounteranion, and an optional phosphine to obtain a polycyclic polymerproduct that contains 100 ppm or less of residual palladium metal priorto purification, wherein y is 1 or 2, R′ represents linear and branchedC₁-C₂₀ alkyl and C₆-C₃₀ haloaryl; L′ represents acetonitrile and adiene; and A′ is a halogen group; wherein said WCA is a borate.
 32. Theprocess of claim 1 wherein said polycycloolefin is selected from amonomer(s) of the formula:

wherein “a” represents a single or double bond, m is an integer from 0to 5, and when “a” is a double bond one of R¹, R² and one of R³, R⁴ isnot present; R¹ to R⁴ independently represent hydrogen, substituted andunsubstituted linear and branched C₁-C₁₀ alkyl, linear and branchedC₁-C₁₀ haloalkyl, substituted and unsubstituted linear and branchedC₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ haloalkenyl, substituted andunsubstituted linear and branched C₂-C₁₀ alkynyl, substituted andunsubstituted C₄-C₁₂ cycloalkyl, substituted and unsubstituted C₄-C₁₂halocycloalkyl, substituted and unsubstituted C₄-C₁₂ cycloalkenyl,substituted and unsubstituted C₄-C₁₂ halocycloalkenyl, substituted andunsubstituted C₆-C₁₂ aryl, substituted and unsubstituted C₆-C₁₂ haloaryland substituted and unsubstituted C₇-C₂₄ aralkyl, R¹ and R² or R³ and R⁴can be taken together to represent a C₁-C₁₀ alkylidenyl group,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵,—(CH₂)_(n)—OC(O)R⁵, —(CH₂)_(n)—C(O)R⁵—(CH₂)_(n)—OC(O)OR⁵,—(CH₂)_(n)SiR⁵, —(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)C(O)OR⁶, and the group:

wherein n independently represents an integer from 0 to 10 and R⁵independently represents hydrogen, linear and branched C₁-C₁₀ alkyl,linear and branched, C₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ alkynyl,C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, and C₇-C₂₄ aralkyl; R⁶ represents aradical selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃,—CH(R⁷)OC(CH₃)₃, dicyclopropylmethyl, dimethylcyclopropylmethyl, or thefollowing cyclic groups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup; R¹ and R⁴ together with the two ring carbon atoms to which theyare attached can represent a substituted or unsubstituted cycloaliphaticgroup containing 4 to 30 ring carbon atoms, a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms andcombinations thereof; R¹ and R⁴ can be taken together to form thedivalent bridging group, —C(O)—Q—(O)C—, which when taken together withthe two ring carbon atoms to which they are attached form a pentacyclicring, wherein Q represents an oxygen atom or the group N(R⁸), wherein R⁸is selected from hydrogen, halogen, linear and branched C₁-C₁₀ alkyl, orC₆-C₁₈ aryl.
 33. The process of claim 31 wherein the palladium metalcomplex is selected from the group consisting of[(1,5-cyclooctadiene)Pd(CH₃)(Cl)] and [(C₆F₅)Pd(CH₃CN)₂(Br)].
 34. Theprocess of claim 33 wherein said optional phosphine is P(C₆H₅)₃, and theWCA salt is the sodium salt oftetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
 35. A process forpreparing a polymer containing polycyclic repeating units comprisingcontacting at least one polycycloolefin monomer with a high activityGroup 10 transition metal catalyst complex of the formula:[(R′)_(z)M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d) to obtain a polymer productthat contains 100 ppm or less of residual Group 10 transition metalprior to purification, wherein [(R′)_(z)M(L′)_(x)(L″)_(y)] is a cationcomplex where M represents a Group 10 transition metal; x is 1 or 2;andy is 0, 1, 2, or 3; and z is 0 or 1, wherein the sum of x, y, and zis 4; [WCA] represents a weakly coordinating counteranion complex; and band d are numbers representing the number of times the cation complexand weakly coordinating counteranion complex are taken to balance theelectronic charge on the overall catalyst complex; R′ represents ananionic hydrocarbyl containing ligand selected from the group consistingof hydrogen, substituted and unsubstituted C₅-C₁₀ cycloalkyl,substituted and unsubstituted linear and branched C₂-C₂₀ alkenyl,substituted and unsubstituted C₆-C₁₅ cycloalkenyl, substituted andunsubstituted allylic ligands or canonical forms thereof, C₆-C₃₀ aryl,C₆-C₃₀ heteroatom containing aryl, and C₇-C₃₀ aralkyl, wherein saidsubstituted hydrocarbyl containing ligands are monosubstituted ormultisubstituted with linear or branched C₁-C₅ alkyl, linear or branchedC₁-C₅ haloalkyl, linear or branched C₂-C₅ alkenyl and haloalkenyl,halogen, sulfur, oxygen, nitrogen, phosphorus, and phenyl optionallymonosubstituted or multisubstituted with linear or branched C₁-C₅ alkyl,linear and branched C₁-C₅ haloalkyl, and halogen; L′ represents a Group15 neutral electron donor ligand; and L″ represents a labile neutralelectron donor ligand.
 36. The process of claim 35 wherein saidpolycycloolefin is selected from a monomer(s) of the formula:

wherein “a” represents a single or double bond, m is an integer from 0to 5, and when “a” is a double bond one of R¹, R² and one of R³, R⁴ isnot present; R¹ to R⁴ independently represent hydrogen, substituted andunsubstituted linear and branched C₁-C₁₀ alkyl, linear and branchedC₁-C₁₀ haloalkyl, substituted and unsubstituted linear and branchedC₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ haloalkenyl, substituted andunsubstituted linear and branched C₂-C₁₀ alkynyl, substituted andunsubstituted C₄-C₁₂ cycloalkyl, substituted and unsubstituted C₄-C₁₂halocycloalkyl, substituted and unsubstituted C₄-C₁₂ cycloalkenyl,substituted and unsubstituted C₄-C₁₂ halocycloalkenyl, substituted andunsubstituted C₆-C₁₂ aryl, substituted and unsubstituted C₆-C₁₂ haloaryland substituted and unsubstituted C₇-C₂₄ aralkyl, R¹ and R² or R³ and R⁴can be taken together to represent a C₁-C₁₀ alkylidenyl group,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵,—(CH₂)_(n)—OC(O)R⁵, —(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵,—(CH₂)_(n)SiR⁵, —(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)C(O)OR⁶, and the group:

wherein n independently represents an integer from 0 to 10 and R⁵independently represents hydrogen, linear and branched C₁-C₁₀ alkyl,linear and branched, C₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ alkynyl,C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, and C₇-C₂₄ aralkyl; R⁶ represents aradical selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃,—CH(R⁷)OC(CH₃)₃, dicyclopropylmethyl, dimethylcyclopropylmethyl, or thefollowing cyclic groups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup; R¹ and R⁴ together with the two ring carbon atoms to which theyare attached can represent a substituted or unsubstituted cycloaliphaticgroup containing 4 to 30 ring carbon atoms, a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms andcombinations thereof, R¹ and R⁴ can be taken together to form thedivalent bridging group, —C(O)—Q—(O)C—, which when taken together withthe two ring carbon atoms to which they are attached form a pentacyclicring, wherein Q represents an oxygen atom or the group N(R⁸), wherein R⁸is selected from hydrogen, halogen, linear and branched C₁-C₁₀ alkyl, orC₆-C₁₈ aryl.
 37. The process of claim 35 wherein said Group 10transition metal M is selected from palladium, platinum or nickel, andsaid Group 15 neutral electron donor ligand L′ is selected from amines,pyridines, arsines, stibines or organophosphorus containing compounds.38. The process of claim 37 wherein said organophosphorus containingligand is selected from a compound of the formula:P(R⁷′)_(g)[X′(R⁷′)_(h)]_(3−g) wherein X′ is oxygen, sulfur, nitrogen, orsilicon; g is 0, 1, 2, or 3; h is 1, 2, or 3, with the proviso that whenX′ is a silicon atom, h is 3, when X′ is an oxygen or sulfur atom h is1, and when X′ is a nitrogen atom, h is 2; R⁷′ is independently selectedfrom hydrogen, linear and branched C₁-C₁₀ alkyl, C₅-C₁₀ cycloalkyl,linear and branched C₁-C₁₀ alkoxy, allyl, linear and branch ed C₂-C₁₀alkenyl, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₆-C₁₂ arylsulfides, C₇-C₁₈aralkyl, cyclic ethers and thioethers, tri(linear and branched C₁-C₁₀alkyl)silyl, tri(C₆-C₁₂ aryl)silyl, tri(linear and branched C₁-C₁₀alkoxy)silyl, triaryloxysilyl, tri(linear and branched C₁-C₁₀alkyl)siloxy, or tri(C₆-C₁₂ aryl)siloxy, wherein each of the foregoingsubstituents can be optionally substituted with linear or branched C₁-C₅alkyl, linear or branched C₁-C₅ haloalkyl, C₁-C₅ alkoxy, halogen, andcombinations thereof; when g is 0 and X′ is oxygen, any two or 3 of R⁷′can be taken together with the oxygen atoms to which they are attachedto form a cyclic moiety; when g is 3 any two of R⁷′ can be takentogether with the phosphorus atom to which they are attached torepresent a phosphacycle of the formula:

wherein R⁷′ is as previously defined and h′ is an integer from 4 to 11.39. The process of claim 37 wherein said organophosphorus containingligand is a bidentate phosphine selected from the formulae:

wherein R⁷′ is as defined and i is 0, 1, 2, or
 3. 40. The process ofclaim 38 wherein g is 3 and R⁷′ is independently selected from the groupconsisting of hydrogen, linear and branched C₁-C₁₀ alkyl, C₅-C₁₀cycloalkyl, linear and branched C₁-C₁₀ alkoxy, allyl, linear andbranched C₂-C₁₀ alkenyl, C₆-C₁₂ aryl, and C₆-C₁₂ aryloxy.
 41. Theprocess of claim 35 wherein the weakly coordinating counteranion complexis selected from the group consisting of borates, aluminates,boratobenzene anions, carborane anions, and halocarborane anions. 42.The process of claim 41 wherein the weakly coordinating anion is aborate or aluminate of the formula: [M′(R²⁴′)(R²⁵′)(R²⁶′)(R²⁷′)] whereinin Formula M′ is boron or aluminum and R²⁴′, R²⁵′, R²⁶′, and R²⁷′independently represent fluorine, linear and branched C₁-C₁₀ alkyl,linear and branched C₁-C₁₀ alkoxy, linear and branched C₃-C₅haloalkenyl, linear and branched C₃-C₁₂ trialkylsiloxy, C₁₈-C₃₆triarylsiloxy, substituted and unsubstituted C₆-C₃₀ aryl, andsubstituted and unsubstituted C₆-C₃₀ aryloxy groups wherein R²⁴′ to R²⁷′can not simultaneously represent alkoxy or aryloxy groups.
 43. Theprocess of claim 42 wherein said substituted aryl and aryloxy groups aremonosubstituted or multisubstituted and said substituents areindependently selected from linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, linear andbranched C₁-C₅ haloalkoxy, linear and branched C₁-C₁₂ trialkylsilyl,C₆-C₁₈ triarylsilyl, or halogen selected from chlorine, bromine, orfluorine.
 44. The process of claim 42 wherein said borate is selectedfrom the group consisting of tetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-i-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,(triphenylsiloxy)tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate.45. The process of claim 42 wherein said aluminate is selected from thegroup consisting of tetrakis(pentafluorophenyl)aluminate,tris(perfluorobiphenyl)fluoroaluminate,(octyloxy)tris(pentafluorophenyl)aluminate,tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, andmethyltris(pentafluorophenyl)aluminate.
 46. The process of claim 41wherein the weakly coordinating anion is a borate or aluminate of theformula: [M′(OR²⁸′)(OR²⁹′)(OR³⁰′)(OR³¹′)] M′ is boron or aluminum, R²⁸′,R²⁹′, R³⁰′, and R³¹′ independently represent linear and branched C₁-C₁₀alkyl, linear and branched C₁-C₁₀ haloalkyl, C₂-C₁₀ haloalkenyl,substituted and unsubstituted C₆-C₃₀ aryl, and substituted andunsubstituted C₇-C₃₀ aralkyl groups, subject to the proviso that atleast three of R²⁸′ to R³¹′ must contain a halogen containingsubstituent; OR²⁸′ and OR²⁹′ can be taken together to form a chelatingsubstituent represented by —O—R³²′—O—, wherein the oxygen atoms arebonded to M′ and R³²′ is a divalent radical selected from substitutedand unsubstituted C₆-C₃₀ aryl or substituted and unsubstituted C₇-C₃₀aralkyl.
 47. The process of claim 46 wherein said substituted aryl andaralkyl groups are monosubstituted or multisubstituted, and saidsubstituents are independently selected from linear and branched C₁-C₅alkyl, linear and branched C₁-C₅ haloalkyl, linear and branched C₁-C₅alkoxy, linear and branched C₁-C₁₀ haloalkoxy, or halogen selected fromchlorine, bromine, or fluorine.
 48. The process of claim 46 wherein saidborate is selected from the group consisting of [B(OC(CF₃)₃)₄]⁻,[B(OC(CF₃)₂(CH₃))₄]⁻, [B(OC(CF₃)₂H)₄]⁻, [B(OC(CF₃)(CH₃)H)₄]⁻, and[B(OCH₂(CF₃)₂)₄]⁻.
 49. The process of claim 46 wherein said aluminate isselected from the group consisting of, [Al(OC(CF₃)₂Ph)₄]⁻,[Al(OC(CF₃)₂C₆H₄CH₃)₄]⁻, [Al(OC(CF₃)₃)₄]⁻, [Al(OC(CF₃)(CH₃)H)₄]⁻,[Al(OC(CF₃)₂H)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]⁻,[Al(OC(CF₃)₂C₆H₄-4-t-butyl)₄]⁻, [Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄,]⁻,[Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,]⁻,[Al(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄]⁻,[Al(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄]⁻, [Al(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄]⁻, and[Al(OC(CF₃)₂C₆F₅)₄]⁻.
 50. The process of claim 36 wherein saidpolycycloolefin monomer is selected from the group consisting of butylnorbornene, triethoxysilyl norbornene, and mixtures thereof.
 51. Theprocess of claim 35 wherein said hydrocarbyl containing ligand isallylic and said cation complex is represented by the formula:

wherein R²⁰′, R²¹′, and R²²′ each independently represent hydrogen,halogen linear and branched C₁-C₅ alkyl, C₅-C₁₀ cycloalkyl, linear andbranched C₁-C₅ alkenyl, C₆-C₃₀ aryl, and C₇-C₃₀ aralkyl, each of theforegoing radicals optionally substituted with a substituent selectedfrom linear and branched C₁-C₅ alkyl, linear and branched C₁-C₅haloalkyl, halogen, and phenyl which can optionally be substituted withlinear and branched C₁-C₅ alkyl, linear and branched C₁-C₅ haloalkyl,and halogen; any two of R²⁰′, R²¹′, and R²²′ can be linked together withthe carbon atoms to which they are attached to form a cyclic ormulticyclic ring, each optionally substituted with linear or branchedC₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, and halogen; M, L′, L″,x and y are as defined previously.
 52. The process of claim 51 whereinL′ is an organophosphorus containing ligand is selected from a compoundof the formula: P(R⁷′)_(g)[X′(R⁷′)_(h)]_(3−g) wherein X′ is oxygen,sulfur, nitrogen, or silicon; g is 0, 1, 2, or 3; h is 1, 2, or 3, withthe proviso that when X′ is a silicon atom, h is 3, when X′ is an oxygenor sulfur atom h is 1, and when X′ is a nitrogen atom, h is 2; R⁷′ isindependently selected from hydrogen, linear and branched C₁-C₁₀ alkyl,C₅-C₁₀ cycloalkyl, linear and branched C₁-C₁₀ alkoxy, allyl, linear andbranched C₂-C₁₀ alkenyl, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₆-C₁₂arylsulfides, C₇-C₁₈ aralkyl, cyclic ethers and thioethers, tri(linearand branched C₁-C₁₀ alkyl)silyl, tri(C₆-C₁₂ aryl)silyl, tri(linear andbranched C₁-C₁₀ alkoxy)silyl, triaryloxysilyl, tri(linear and branchedC₁-C₁₀ alkyl)siloxy, or tri(C₆-C₁₂ aryl)siloxy, wherein each of theforegoing substituents can be optionally substituted with linear orbranched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, C₁-C₅ alkoxy,halogen, and combinations thereof, when g is 0 and X′ is oxygen, any twoor 3 of R⁷′ can be taken together with the oxygen atoms to which theyare attached to form a cyclic moiety; when g is 3 any two of R⁷′ can betaken together with the phosphorus atom to which they are attached torepresent a phosphacycle of the formula:

wherein R⁷′ is as previously defined and h′ is an integer from 4 to 11.53. The process of claim 52 wherein said organophosphorus containingligand is a phosphine selected from the group consisting oftrimethylphosphine, triethylphosphine, tri-n-propylphosphine,triisopropylphosphine, tri-n-butylphosphine, tri-sec-butylphosphine,tri-i-butylphosphine, tri-t-butylphosphine, tricyclopentylphosphine,triallylphosphine, tricyclohexylphosphine, triphenylphosphine,trinaphthylphosphine, tri-p-tolylphosphine, tri-o-tolylphosphine,tri-m-tolylphosphine, tribenzylphosphine,tri(p-trifluoromethylphenyl)phosphine, tris(trifluoromethyl)phosphine,tri(p-fluorophenyl)phosphine, tri(p-trifluoromethylphenyl)phosphine,allyldiphenylphosphine, benzyldiphenylphosphine, bis(2-furyl)phosphine,bis(4-methoxyphenyl)phenylphosphine, bis(4-methylphenyl)phosphine,bis(3,5-bis(trifluoromethyl)phenyl)phosphine,t-butylbis(trimethylsilyl)phosphine, t-butyldiphenylphosphine,cyclohexyldiphenylphosphine, diallylphenylphosphine, dibenzylphosphine,dibutylphenylphosphine, dibutylphosphine, di-t-butylphosphine,dicyclohexylphosphine, diethylphenylphosphine, di-i-butylphosphine,dimethylphenylphosphine, dimethyl(trimethylsilyl)phosphine,diphenylphosphine, diphenylpropylphosphine, diphenyl(p-tolyl)phosphine,diphenyl(trimethylsilyl)phosphine, diphenylvinylphosphine,divinylphenylphosphine, ethyldiphenylphosphine,(2-methoxyphenyl)methylphenylphosphine, tri-n-octylphosphine,tris(3,5-bis(trifluoromethyl)phenyl)phosphine,tris(3-chlorophenyl)phosphine, tris(4-chlorophenyl)phosphine,tris(2,6-dimethoxyphenyl)phosphine, tris(3-fluorophenyl)phosphine,tris(2-furyl)phosphine, tris(2-methoxyphenyl)phosphine,tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine,tris(3-methoxypropyl)phosphine , tris(2-thienyl)phosphine,tris(2,4,6-trimethylphenyl)phosphine, tris(trimethylsilyl)phosphine,isopropyldiphenylphosphine, dicyclohexylphenylphosphine,(+)-neomenthyldiphenylphosphine, tribenzylphosphine,diphenyl(2-methoxyphenyl)phosphine,diphenyl(pentafluorophenyl)phosphine,bis(pentafluorophenyl)phenylphosphine, andtris(pentafluorophenyl)phosphine.
 54. A process for preparing a polymercontaining polycyclic repeating units in the substantial absence ofsolvent comprising contacting at least one polycycloolefin monomer witha Group 10 transition metal containing procatalyst complex of theformula [R′M(L′)_(x)(A′)], a weakly coordinating anion salt containing acation complex and a weakly coordinating anion complex of the formula[C(L″)_(z)″]_(b)″[WCA]_(d)″, and an optional labile neutral electrondonor compound, wherein M represents a Group 10 transition metalselected from the group consisting of nickel, platinum, and palladium;R′ is an anionic hydrocarbyl containing ligand; L′ represents a Group 15neutral electron donor ligand; A′ represents an anionic leaving groupthat can be displaced by said weakly coordinating anion complex; L″represents a labile neutral electron donor ligand compound; C representsa cation selected from the group consisting of a proton, a Group 1 metalcation, a Group 2 metal cation, and an organic group containing cation;WCA represents a weakly coordinating anion complex; x is 1 or 2; z″ isan integer from 0 to 8; and b″ and d″ represent the number of times thecation and anion complex of said weakly coordinating anion salt aretaken to balance the charge on said salt.
 55. A process for preparing apolymer containing polycyclic repeating units in the substantial absenceof solvent comprising contacting at least one polycycloolefin monomerwith a Group 10 transition metal containing procatalyst complex of theformula [M(A′)₂], a Group 15 neutral electron donor compound, and aweakly coordinating anion salt containing a cation complex and a weaklycoordinating anion complex of the formula [C(L″)_(z″)]_(b)″[WCA]_(d)″,wherein M represents a Group 10 transition metal selected from the groupconsisting of nickel, platinum, and palladium; A′ represents an anionicleaving group that can be displaced by said weakly coordinating anioncomplex; C represents a cation selected from the group consisting of aproton, a Group 1 metal cation, a Group 2 metal cation, and an organicgroup containing cation; WCA represents a weakly coordinating anioncomplex; z″ is an integer from 0 to 8; and b″ and d″ represent thenumber of times the cation and anion complex of said weakly coordinatinganion salt are taken to balance the charge on said salt.
 56. The processof claim 54 wherein L′ is selected from the group consisting of amines,pyridines, arsines, stibines and organophosphorus containing compounds.57. The process of claim 55 wherein said Group 15 neutral electron donorcompound is selected from the group consisting of amines, pyridines,arsines, stibines and organophosphorus containing compounds.
 58. Theprocess of claim 56 or 57 wherein said organophosphorus containingligand is selected from a compound of the formula:P(R⁷′)_(g)[X′(R⁷′)_(h)]_(3−g) wherein X′ is oxygen, sulfur, nitrogen, orsilicon; g is 0, 1, 2, or 3; h is 1, 2, or 3, with the proviso that whenX′ is a silicon atom, h is 3, when X′ is an oxygen or sulfur atom h is1, and when X′ is a nitrogen atom, h is 2; R⁷′ is independently selectedfrom hydrogen, linear and branched C₁-C₁₀ alkyl, C₅-C₁₀ cycloalkyl,linear and branched C₁-C₁₀ alkoxy, allyl, linear and branched C₂-C₁₀alkenyl, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₆-C₁₂ arylsulfides, C₇-C₁₈aralkyl, cyclic ethers and thioethers, tri(linear and branched C₁-C₁₀alkyl)silyl, tri(C₆-C₁₂ aryl)silyl, tri(linear and branched C₁-C₁₀alkoxy)silyl, triaryloxysilyl, tri(linear and branched C₁-C₁₀alkyl)siloxy, and tri(C₆-C₁₂ aryl)siloxy, wherein each of the foregoingsubstituents can be optionally substituted with linear or branched C₁-C₅alkyl, linear or branched C₁-C₅ haloalkyl, C₁-C₅ alkoxy, halogen, orcombinations thereof; when g is 0 and X′ is oxygen, any two or 3 of R⁷′can be taken together with the oxygen atoms to which they are attachedto form a cyclic ether; when g is 3 any two of R⁷′ can be taken togetherwith the phosphorus atom to which they are attached to represent aphosphacycle of the formula:

wherein R⁷′ is as previously defined and h′ is an integer from 4 to 11.59. The process of claim 56 or 57 wherein said organophosphoruscontaining ligand is a bidentate phosphine selected from the formulae:

wherein R⁷′ is as previously defined and i is 0, 1, 2, or
 3. 60. Theprocess of claim 58 wherein said organophosphorus containing ligand is aphosphine selected from the group consisting of trimethylphosphine,triethylphosphine, tri-n-propylphosphine, triisopropylphosphine,tri-n-butylphosphine, tri-sec-butylphosphine, tri-i-butylphosphine,tri-t-butylphosphine, tricyclopentylphosphine, triallylphosphine,tricyclohexylphosphine, triphenylphosphine, trinaphthylphosphine,tri-p-tolylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine,tribenzylphosphine, tri(p-trifluoromethylphenyl)phosphine,tris(trifluoromethyl)phosphine, tri(p-fluorophenyl)phosphine,tri(p-trifluoromethylphenyl)phosphine, allyldiphenylphosphine,benzyldiphenylphosphine, bis(2-furyl)phosphine,bis(4-methoxyphenyl)phenylphosphine, bis(4-methylphenyl)phosphine,bis(3,5-bis(trifluoromethyl)phenyl)phosphine,t-butylbis(trimethylsilyl)phosphine, t-butyldiphenylphosphine,cyclohexyldiphenylphosphine, diallylphenylphosphine, dibenzylphosphine,dibutylphenylphosphine, dibutylphosphine, di-t-butylphosphine,dicyclohexylphosphine, diethylphenylphosphine, di-i-butylphosphine,dimethylphenylphosphine, dimethyl(trimethylsilyl)phosphine,diphenylphosphine, diphenylpropylphosphine, diphenyl(p-tolyl)phosphine,diphenyl(trimethylsilyl)phosphine, diphenylvinylphosphine,divinylphenylphosphine, ethyldiphenylphosphine,(2-methoxyphenyl)methylphenylphosphine, tri-n-octylphosphine,tris(3,5-bis(trifluoromethyl)phenyl)phosphine,tris(3-chlorophenyl)phosphine, tris(4-chlorophenyl)phosphine,tris(2,6-dimethoxyphenyl)phosphine, tris(3-fluorophenyl)phosphine,tris(2-furyl)phosphine, tris(2-methoxyphenyl)phosphine,tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine,tris(3-methoxypropyl)phosphine, tris(2-thienyl)phosphine,tris(2,4,6-trimethylphenyl)phosphine, tris(trimethylsilyl)phosphine,isopropyldiphenylphosphine, dicyclohexylphenylphosphine,(+)-neomenthyldiphenylphosphine, tribenzylphosphine,diphenyl(2-methoxyphenyl)phosphine,diphenyl(pentafluorophenyl)phosphine,bis(pentafluorophenyl)phenylphosphine, andtris(pentafluorophenyl)phosphine.
 61. The process of claim 54 or 55wherein said anionic leaving group is selected from the group consistingof halogen, nitrate, triflate, triflimide trifluoroacetate, tosylate,AlBr₄ ⁻, AlF₄ ⁻, AlCl₄ ⁻, AlF₃O₃SCF₃ ⁻, AsCl₆ ⁻, SbCl₆ ⁻, SbF₆ ⁻, PF₆ ⁻,BF₄ ⁻, ClO₄ ⁻, HSO₄ ⁻, carboxylates, acetates, acetylacetonates,carbonates, aluminates, borates, hydrocarbyl and halogenated hydrocarbylselected from hydride, linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, C₅-C₁₀ cycloalkyl, C₅-C₁₀ cyclohaloalkyl,C₆-C₁₀ aryl, or C₆-C₁₀ haloaryl, wherein said cyclohaloalkyl andhaloaryl groups are monosubstituted or multisubstituted with a halogengroup selected from bromine, chlorine, fluorine, or iodine.
 62. Theprocess of claim 54 or 55 wherein said weakly coordinating anion salt isa salt of a borate or aluminate of the formula:[C]_(b″)[M′(R²⁴′)(R²⁵′)(R²⁶′)(R²⁷′)]_(d)″ wherein C represents a cationselected from the group consisting of a proton, a Group 1 metal cation,a Group 2 metal cation, and an organic group containing cation; b″ andd″ represent the number of times the cation and anion complex of saidweakly coordinating anion salt are taken to balance the charge on saidsalt; M′ is boron or aluminum and R²⁴′, R²⁵′, R²⁶′, and R²⁷′independently represent fluorine, linear and branched C₁-C₁₀ alkyl,linear and branched C₁-C₁₀ alkoxy, linear and branched C₃-C₅haloalkenyl, linear and branched C₃-C₁₂ trialkylsiloxy, C₁₈-C₃₆triarylsiloxy, substituted and unsubstituted C₆-C₃₀ aryl, andsubstituted and unsubstituted C₆-C₃₀ aryloxy groups wherein R²⁴′ to R²⁷′can not simultaneously represent alkoxy or aryloxy groups.
 63. Theprocess of claim 62 wherein said substituted aryl and aryloxy groups aremonosubstituted or multisubstituted and said substituents areindependently selected from linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, linear andbranched C₁-C₅ haloalkoxy, linear and branched C₁-C₁₂ trialkylsilyl,C₆-C₁₈ triarylsilyl, or halogen selected from chlorine, bromine, orfluorine.
 64. The process of claim 62 wherein said weakly coordinatinganion salt is selected from the group consisting of lithiumtetrakis(2-fluorophenyl)borate, sodium tetrakis(2-fluorophenyl)borate,silver tetrakis(2-fluorophenyl)borate, thalliumtetrakis(2-fluorophenyl)borate, lithium tetrakis(3-fluorophenyl)borate,sodium tetrakis(3-fluorophenyl)borate, silvertetrakis(3-fluorophenyl)borate, thallium tetrakis(3-fluorophenyl)borate,ferrocenium tetrakis(3-fluorophenyl)borate, ferroceniumtetrakis(pentafluorophenyl)borate, lithium tetrakis(4-fluorophenyl)borate, sodium tetrakis(4-fluorophenyl)borate, silvertetrakis(4-fluorophenyl)borate, thallium tetrakis(4-fluorophenyl)borate,lithium tetrakis(3,5-difluorophenyl)borate, sodiumtetrakis(3,5-difluorophenyl)borate, thalliumtetrakis(3,5-difluorophenyl)borate, trityltetrakis(3,5-difluorophenyl)borate, 2,6-dimethylaniliniumtetrakis(3,5-difluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium(diethyl ether)tetrakis(pentafluorophenyl)borate, lithium(diethyl ether)_(2.5)tetrakis(pentafluorophenyl)borate, lithiumtetrakis(2,3,4,5-tetrafluorophenyl)borate, lithiumtetrakis(3,4,5,6-tetrafluorophenyl)borate, lithiumtetrakis(1,2,2-trifluoroethylenyl)borate, lithiumtetrakis(3,4,5-trifluorophenyl)borate, lithiummethyltris(perfluorophenyl)borate, lithiumphenyltris(perfluorophenyl)borate, lithium tris(isopropanol)tetrakis(pentafluorophenyl)borate, lithium tetrakis(methanol)tetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, tris(toluene)silvertetrakis(pentafluorophenyl)borate, tris(xylene)silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, trityltetrakis(4-triisopropylsilyltetrafluorophenyl)borate, trityltetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, thalliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, 2,6-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate lithium(triphenylsiloxy)tris(pentafluorophenyl)borate, sodium(triphenylsiloxy)tris(pentafluorophenyl)borate, sodiumtetrakis(2,3,4,5-tetrafluorophenyl)borate, sodiumtetrakis(3,4,5,6-tetrafluorophenyl)borate, sodiumtetrakis(1,2,2-trifluoroethylenyl)borate, sodiumtetrakis(3,4,5-trifluorophenyl)borate, sodiummethyltris(perfluorophenyl)borate, sodiumphenyltris(perfluorophenyl)borate, thalliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, thalliumtetrakis(3,4,5,6-tetrafluorophenyl)borate, thalliumtetrakis(1,2,2-trifluoroethylenyl)borate, thalliumtetrakis(3,4,5-trifluorophenyl)borate, sodiummethyltris(perfluorophenyl)borate, thalliumphenyltris(perfluorophenyl)borate, trityltetrakis(2,3,4,5-tetrafluorophenyl)borate, trityltetrakis(3,4,5,6-tetrafluorophenyl)borate, trityltetrakis(1,2,2-trifluoroethylenyl)borate, trityltetrakis(3,4,5-trifluorophenyl)borate, tritylmethyltris(pentafluorophenyl)borate, tritylphenyltris(perfluorophenyl)borate, silvertetrakis[3,5-bis(trifluoromethyl)phenyl]borate, silver(toluene)tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, thalliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, lithium(hexyltris(pentafluorophenyl)borate, lithiumtriphenylsiloxytris(pentafluorophenyl)borate,lithium(octyloxy)tris(pentafluorophenyl)borate, lithiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate,sodium(octyloxy)tris(pentafluorophenyl)borate, sodiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, potassiumtetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate,potassium(octyloxy)tris(pentafluorophenyl)borate, potassiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, magnesiumtetrakis(pentafluorophenyl)borate, magnesium(octyloxy)tris(pentafluorophenyl)borate, magnesiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, calciumtetrakis(pentafluorophenyl)borate, calcium(octyloxy)tris(pentafluorophenyl)borate, calciumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, lithiumtetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,sodiumtetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,silvertetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,thalliumtetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,lithiumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,sodiumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,silvertetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,thalliumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,lithiumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,sodiumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,silvertetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,thalliumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,trimethylsilylium tetrakis(pentafluorophenyl)borate, trimethylsilyliurnetherate tetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, triphenylsilyliumtetrakis(pentafluorophenyl)borate, tris(mesityl)silyliumtetrakis(pentafluorophenyl)borate, tribenzylsilyliumtetrakis(pentafluorophenyl)borate, trimethylsilyliummethyltris(pentafluorophenyl)borate, triethylsilyliummethyltris(pentafluorophenyl)borate, triphenylsilyliummethyltris(pentafluorophenyl)borate, tribenzylsilylium methyltris(pentafluorophenyl)borate, trimethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, tribenzylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, trimethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, trimethylsilyliumtetrakis(3,4,5-trifluorophenyl)borate, tribenzylsilyliumtetrakis(3,4,5-trifluorophenyl)aluminate, triphenylsilyliummethyltris(3,4,5-trifluorophenyl)aluminate, triethylsilyliumtetrakis(1,2,2-trifluoroethenyl)borate, tricyclohexylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, dimethyloctadecylsilyliumtetrakis(pentafluorophenyl)borate, tris(trimethyl)silyl)silyliummethyltri(2,3,4,5-tetrafluorophenyl)borate,2,2′-dimethyl-1,1′-binaphthylmethylsilyliumtetrakis(pentafluorophenyl)borate,2,2′-dimethyl-1,1′-binaphthylmethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, lithiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate, trityl(perfluorobiphenyl)fluoroaluminate,lithium(octyloxy)tris(pentafluorophenyl)aluminate, lithiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, sodiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate,sodium(octyloxy)tris(pentafluorophenyl)aluminate, sodiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, potassiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate, potassium(octyloxy)tris(pentafluorophenyl)aluminate, potassiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, magnesiumtetrakis(pentafluorophenyl)aluminate,magnesium(octyloxy)tris(pentafluorophenyl)aluminate, magnesiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, calciumtetrakis(pentafluorophenyl)aluminate, calcium(octyloxy)tris(pentafluorophenyl)aluminate, and calciumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate.
 65. The process ofclaim 54 or 55 wherein said weakly coordinating anion salt is a salt ofa borate or aluminate of the formula:[C]_(b″)[M′(OR²⁸′)(OR²⁹′)(OR³⁰′)(OR³¹′)]_(d)″ wherein C represents acation selected from the group consisting of a proton, a Group 1 metalcation, a Group 2 metal cation, and an organic group containing cation;b″ and d″ represent the number of times the cation and anion complex ofsaid weakly coordinating anion salt are taken to balance the charge onsaid salt; M′ is boron or aluminum, R²⁸′, R²⁹′, R³⁰′, and R³¹′independently represent linear and branched C₁-C₁₀ alkyl, linear andbranched C₁-C₁₀ haloalkyl, C₂-C₁₀ haloalkenyl, substituted andunsubstituted C₆-C₃₀ aryl, and substituted and unsubstituted C₇-C₃₀aralkyl groups, subject to the proviso that at least three of R²⁸′ toR³¹′ must contain a halogen containing substituent; OR²⁸′ and OR²⁹′ canbe taken together to form a chelating substituent represented by—O—R³²′—O—, wherein the oxygen atoms are bonded to M′ and R³²′ is adivalent radical selected from substituted and unsubstituted C₆-C₃₀ aryland substituted and unsubstituted C₇-C₃₀ aralkyl.
 66. The process ofclaim 65 wherein said substituted aryl and aralkyl groups aremonosubstituted or multisubstituted, and said substituents areindependently selected from linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, linear andbranched C₁-C₁₀ haloalkoxy, or halogen selected from chlorine, bromine,or fluorine.
 67. The process of claim 65 wherein said weaklycoordinating anion salt is selected from the group consisting ofLiB(OC(CF₃)₃)₄, LiB(OC(CF₃)₂(CH₃))₄, LiB(OC(CF₃)₂H)₄,LiB(OC(CF₃)(CH₃)H)₄, TlB(OC(CF₃)₃)₄, TlB(OC(CF₃)₂H)₄,TlB(OC(CF₃)(CH₃)H)₄, TlB(OC(CF₃)₂(CH₃))₄, (Ph₃C)B(OC(CF₃)₃)₄,(Ph₃C)B(OC(CF₃)₂(CH₃))₄, (Ph₃C)B(OC(CF₃)₂H)₄, (Ph₃C)B(OC(CF₃)(CH₃)H)₄,AgB(OC(CF₃)₃)₄, AgB(OC(CF₃)₂H)₄, AgB(OC(CF₃)(CH₃)H)₄, LiB(O₂C₆F₄)₂,TlB(O₂C₆F₄)₂, Ag(toluene)₂B(O₂C₆F₄)₂, and Ph₃CB(O₂C₆F₄)₂,LiB(OCH₂(CF₃)₂)₄, [Li(HOCH₃)₄]B(O₂C₆Cl₄)₂, [Li(HOCH₃)₄]B(O₂C₆F₄)₂,[Ag(toluene)₂]B(O₂C₆Cl₄)₂, LiB(O₂C₆Cl₄)₂, (LiAl(OC(CF₃)₂Ph)₄),(TlAl(OC(CF₃)₂Ph)₄), (AgAl(OC(CF₃)₂Ph)₄), (Ph₃CAl(OC(CF₃)₂Ph)₄,(LiAl(OC(CF₃)₂C₆H₄CH₃)₄), (ThAl(OC(CF₃)₂C₆H₄CH₃)₄),(AgAl(OC(CF₃)₂C₆H₄CH₃)₄), (Ph₃CAl(OC(CF₃)₂C₆H₄CH₃)₄), LiAl(OC(CF₃)₃)₄,TlAl(OC(CF₃)₃)₄, AgAl(OC(CF₃)₃)₄, Ph₃CAl(OC(CF₃)₃)₄,LiAl(OC(CF₃)(CH₃)H)₄, TlAl(OC(CF₃)(CH₃)H)₄, AgAl(OC(CF₃)(CH₃)H)₄,Ph₃CAl(OC(CF₃)(CH₃)H)₄, LiAl(OC(CF₃)₂H)₄, TlAl(OC(CF₃)₂H)₄,AgAl(OC(CF₃)₂H)₄, Ph₃CAl(OC(CF₃)₂H)₄, LiAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄,TlAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄, AgAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄, LiAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄,TlAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄, AgAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄, LiAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄,TlAl(OC(CF₃)₂C₆H₄-4-Si Me₃)₄, AgAl(OC(CF₃)₂C₆H₄-4-Si Me₃)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-Si Me₃)₄, LiAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,TlAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄, AgAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,LiAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,TlAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,AgAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,Ph₃CAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,LiAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄, TlAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄,AgAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄, Ph₃CAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄,LiAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄, TlAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄,AgAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄, Ph₃CAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄,LiAl(OC(CF₃)₂C₆F₅)₄, TlAl(OC(CF₃)₂C₆F₅)₄, AgAl(OC(CF₃)₂C₆F₅)₄, andPh₃CAl(OC(CF₃)₂C₆F₅)₄.
 68. The process of claim 54 or 55 wherein saidpolycycloolefin is selected from a monomer(s) of the formula:

wherein “a” represents a single or double bond, m is an integer from 0to 5, and when “a” is a double bond one of R¹, R² and one of R³, R⁴ isnot present; R¹ to R⁴ independently represent hydrogen, substituted andunsubstituted linear and branched C₁-C₁₀ alkyl, linear and branchedC₁-C₁₀ haloalkyl, substituted and unsubstituted linear and branchedC₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ haloalkenyl, substituted andunsubstituted linear and branched C₂-C₁₀ alkynyl, substituted andunsubstituted C₄-C₁₂ cycloalkyl, substituted and unsubstituted C₄-C₁₂halocycloalkyl, substituted and unsubstituted C₄-C₁₂ cycloalkenyl,substituted and unsubstituted C₄-C₁₂ halocycloalkenyl, substituted andunsubstituted C₆-C₁₂ aryl, substituted and unsubstituted C₆-C₁₂ haloaryland substituted and unsubstituted C₇-C₂₄ aralkyl, R¹ and R² or R³ and R⁴can be taken together to represent a C₁-C₁₀ alkylidenyl group,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵,—(CH₂)_(n)—OC(O)R⁵, —(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵,—(CH₂)_(n)SiR⁵, —(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)C(O)OR⁶, and the group:

wherein n independently represents an integer from 0 to 10 and R⁵independently represents hydrogen, linear and branched C₁-C₁₀ alkyl,linear and branched, C₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ alkynyl,C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, and C₇-C₂₄ aralkyl; R⁶ represents aradical selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃,—CH(R⁷)OC(CH₃)₃, dicyclopropylmethyl, dimethylcyclopropylmethyl, or thefollowing cyclic groups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup; R¹ and R⁴ together with the two ring carbon atoms to which theyare attached can represent a substituted or unsubstituted cycloaliphaticgroup containing 4 to 30 ring carbon atoms, a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms andcombinations thereof; R¹ and R⁴ can be taken together to form thedivalent bridging group, —C(O)—Q—(O)C—, which when taken together withthe two ring carbon atoms to which they are attached form a pentacyclicring, wherein Q represents an oxygen atom or the group N(R⁸), wherein R⁸is selected from hydrogen, halogen, linear and branched C₁-C₁₀ alkyl, orC₆-C₁₈ aryl.
 69. The process of claim 68 further comprising at least onemultifunctional polycycloolefinic crosslinking monomer.
 70. The processof claim 69 wherein said multifunctional polycycloolefinic crosslinkingmonomer contains at least two polymerizable norbornene-type double bondsin its structure.
 71. The process of claim 70 wherein said crosslinkingmonomer is selected from the group consisting of the formulae:

and mixtures thereof, wherein m independently is an integer from 0 to 5and R⁹ is a divalent radical selected from alkylene, aromatic, or etherradicals.
 72. The process of claim 1, 35, 54, or 55 wherein saidpolycycloolefin monomer is a deuterated norbornene-type monomer.
 73. Theprocess of claim 72 wherein said deuterated norbornene-type monomer isrepresented by the formula:

wherein R^(D) is deuterium, “i” is an integer ranging from 0 to 6, R¹and R² independently represent a hydrocarbyl radical, and R^(1D) andR^(2D) may or may not be present and independently represent a deuteriumatom or a deuterium enriched hydrocarbyl group containing at least onedeuterium atom, with the proviso that when “i” is 0, at least one ofR^(1D) and R^(2D) must be present.
 74. The process of claim 73 whereinR¹ and R² independently represent linear and branched C₁-C₁₀ alkyl,linear and branched C₂-C₁₀ alkenyl, and C₆-C₁₂ aryl.
 75. The process ofclaim 73 wherein said deuterated hydrocarbyl group is selected fromlinear or branched C₁-C₁₀ alkyl, and at least 40 percent of the hydrogenatoms on said hydrocarbyl groups are replaced by deuterium.
 76. Theprocess of claim 70 or 74 wherein said polymer is post cured an elevatedtemperature for a time period of at least 1 hour.
 77. A process forpreparing a polymer containing polycyclic repeating units comprisingcontacting at least one polycycloolefin monomer in the substantialabsence of solvent with a Group 10 transition metal containingprocatalyst complex of the formula: [R′M(L′)_(x)(A′)] a weaklycoordinating anion salt containing a cation complex and a weaklycoordinating anion complex of the formula [C(L″)_(z)″]_(b)″[WCA]_(d)″,and an optional labile neutral electron donor compound, wherein Mrepresents a Group 10 transition metal selected from the groupconsisting of nickel, platinum, and palladium; R′ represents hydrogen oran allylic ligand; L′ represents a Group 15 neutral electron donorligand; A′ represents an anionic leaving group that can be displaced bysaid weakly coordinating anion complex; L″ represents a labile neutralelectron donor ligand compound; C represents a cation selected from thegroup consisting of a proton, a Group 1 metal cation, a Group 2 metalcation, and an organic group containing cation; WCA represents a weaklycoordinating anion complex; x is 1 or 2; z″ is an integer from 0 to 8;and b″ and d″ represent the number of times the cation and anion complexof said weakly coordinating anion salt are taken to balance the chargeon said salt.
 78. The process of claim 77 wherein said allylic ligand isrepresented by the formula:

wherein R²⁰′, R²¹′, and R²²′ each independently represent hydrogen,halogen, linear and branched C₁-C₅ alkyl, C₅-C₁₀ cycloalkyl, linear andbranched C₁-C₅ alkenyl, C₆-C₃₀ aryl, C₇-C₃₀ aralkyl, each optionallysubstituted with a substituent selected from linear and branched C₁-C₅alkyl, linear and branched C₁-C₅ haloalkyl, halogen, and phenyl whichcan optionally be substituted with linear and branched C₁-C₅ alkyl,linear and branched C₁-C₅ haloalkyl, and halogen. Any two of R²⁰′, R²¹′,and R²²′ can be linked together with the carbon atoms to which they areattached to form a cyclic or multicyclic ring, each optionallysubstituted with linear or branched C₁-C₅ alkyl, linear or branchedC₁-C₅ haloalkyl, and halogen.
 79. The process of claim 77 or 78 whereinL′ is selected from the group consisting of amines, pyridines, arsines,stibines and organophosphorus containing compounds.
 80. The process ofclaim 79 wherein said organophosphorus containing ligand is selectedfrom a compound of the formula: P(R⁷′)_(g)[X′(R⁷′)_(h)]_(3−g) wherein X′is oxygen, sulfur, nitrogen, or silicon; g is 0, 1, 2, or 3; h is 1, 2,or 3, with the proviso that when X′ is a silicon atom, h is 3, when X′is an oxygen or sulfur atom h is 1, and when X′ is a nitrogen atom, h is2; R⁷′ is independently selected from hydrogen, linear and branchedC₁-C₁₀ alkyl, C₅-C₁₀ cycloalkyl, linear and branched C₁-C₁₀ alkoxy,allyl, linear and branched C₂-C₁₀ alkenyl, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy,C₆-C₁₂ arylsulfides, C₇-C₁₈ aralkyl, cyclic ethers and thioethers,tri(linear and branched C₁-C₁₀ alkyl)silyl, tri(C₆-C₁₂ aryl)silyl,tri(linear and branched C₁-C₁₀ alkoxy)silyl, triaryloxysilyl, tri(linearand branched C₁-C₁₀ alkyl)siloxy, or tri(C₆-C₁₂ aryl)siloxy, whereineach of the foregoing substituents can be optionally substituted withlinear or branched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl,C₁-C₅ alkoxy, halogen, and combinations thereof; when g is 0 and X′ isoxygen, any two or 3 of R⁷′ can be taken together with the oxygen atomsto which they are attached to form a cyclic moiety; when g is 3 any twoof R⁷′ can be taken together with the phosphorus atom to which they areattached to represent a phosphacycle of the formula:

wherein R⁷′ is as previously defined and h′ is an integer from 4 to 11.81. The process of claim 80 wherein said organophosphorus containingligand is a bidentate phosphine selected from the formulae:

wherein R⁷′ is as previously defined and i is 0, 1, 2, or
 3. 82. Theprocess of claim 81 wherein g is 3 and R⁷′ is independently selectedfrom the group consisting of hydrogen, linear and branched C₁-C₁₀ alkyl,C₅-C₁₀ cycloalkyl, linear and branched C₁-C₁₀ alkoxy, allyl, linear andbranched C₂-C₁₀ alkenyl, substituted and unsubstituted C₆-C₁₂ aryl, andsubstituted and unsubstituted C₆-C₁₂ aryloxy.
 83. The process of claim82 wherein said wherein said aryl and aryloxy groups are monosubstitutedor multisubstituted and said substituents are selected from the groupconsisting of linear and branched C₁-C₁₀ alkyl, halogen, aryl, andcombinations thereof.
 84. The process of claim 83 wherein R⁷′ isselected from the group consisting of cyclohexyl, isopropyl, phenyl,naphthyl, o-tolyl, and combinations thereof.
 85. The process of claim 77or 78 wherein A′ is selected from the group consisting of halogen,nitrate, triflate, triflimide, trifluoroacetate, and tosylate.
 86. Theprocess of claim 77 or 78 wherein said weakly coordinating anion salt isa salt of a borate or aluminate of the formula:[C]_(b″)[M′(R²⁴′)(R²⁵′)(R²⁶′)(R²⁷′)]_(d)″ wherein C represents a cationselected from the group consisting of a proton, a Group 1 metal cation,a Group 2 metal cation, and an organic group containing cation; b″ andd″ represent the number of times the cation and anion complex of saidweakly coordinating anion salt are taken to balance the charge on saidsalt; M′ is boron or aluminum and R²⁴′, R²⁵′, R²⁶′, and R²⁷′independently represent fluorine, linear and branched C₁-C₁₀ alkyl,linear and branched C₁-C₁₀ alkoxy, linear and branched C₃-C₅haloalkenyl, linear and branched C₃-C₁₂ trialkylsiloxy, C₁₈-C₃₆triarylsiloxy, substituted and unsubstituted C₆-C₃₀ aryl, andsubstituted and unsubstituted C₆-C₃₀ aryloxy groups wherein R²⁴′ to R²⁷′can not simultaneously represent alkoxy or aryloxy groups.
 87. Theprocess of claim 86 wherein said substituted aryl and aryloxy groups arebe monosubstituted or multisubstituted and said substituents areindependently selected from linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, linear andbranched C₁-C₅ haloalkoxy, linear and branched C₁-C₁₂ trialkylsilyl,C₆-C₁₈ triarylsilyl, or halogen selected from chlorine, bromine, orfluorine.
 88. The process of claim 77 or 78 wherein said weaklycoordinating anion salt is a salt of a borate or aluminate of theformula: [C]_(b″)[M′(OR²⁸′)(OR²⁹′)(OR³⁰′)(OR³¹′)]_(d)″ wherein Crepresents a cation selected from the group consisting of a proton, aGroup 1 metal cation, a Group 2 metal cation, and an organic groupcontaining cation; b″ and d″ represent the number of times the cationand anion complex of said weakly coordinating anion salt are taken tobalance the charge on said salt; M′ is boron or aluminum, R²⁸′, R²⁹′,R³⁰′, and R31′ independently represent linear and branched C₁-C₁₀ alkyl,linear and branched C₁-C₁₀ haloalkyl, C₂-C₁₀ haloalkenyl, substitutedand unsubstituted C₆-C₃₀ aryl, and substituted and unsubstituted C₇-C₃₀aralkyl groups, subject to the proviso that at least three of R²⁸′ toR³¹′ must contain a halogen containing substituent; OR²⁸′ and OR²⁹′ canbe taken together to form a chelating substituent represented by—O—R³²′—O—, wherein the oxygen atoms are bonded to M′ and R³²′ is adivalent radical selected from substituted and unsubstituted C₆-C₃₀ arylor substituted and unsubstituted C₇-C₃₀ aralkyl.
 89. The process ofclaim 88 wherein said substituted aryl and aralkyl groups aremonosubstituted or multisubstituted, and said substituents areindependently selected from linear and branched C₁-C₅ alkyl, linear andbranched C₁-C₅ haloalkyl, linear and branched C₁-C₅ alkoxy, linear andbranched C₁-C₁₀ haloalkoxy, or halogen selected from chlorine, bromine,or fluorine.
 90. The process of claim 77 or 78 wherein saidpolycycloolefin is selected from a monomer(s) of the formula:

wherein “a” represents a single or double bond, m is an integer from 0to 5, and when “a” is a double bond one of R¹, R² and one of R³, R⁴ isnot present; R¹ to R⁴ independently represent hydrogen, substituted andunsubstituted linear and branched C₁-C₁₀ alkyl, linear and branchedC₁-C₁₀ haloalkyl, substituted and unsubstituted linear and branchedC₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ haloalkenyl, substituted andunsubstituted linear and branched C₂-C₁₀ alkynyl, substituted andunsubstituted C₄-C₁₂ cycloalkyl, substituted and unsubstituted C₄-C₁₂halocycloalkyl, substituted and unsubstituted C₄-C₁₂ cycloalkenyl,substituted and unsubstituted C₄-C₁₂ halocycloalkenyl, substituted andunsubstituted C₆-C₁₂ aryl, substituted and unsubstituted C₆-C₁₂ haloaryland substituted and unsubstituted C₇-C₂₄ aralkyl, R¹ and R² or R³ and R⁴can be taken together to represent a C₁-C₁₀ alkylidenyl group,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵,—(CH₂)_(n)—OC(O)R⁵, —(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵,—(CH₂)_(n)SiR⁵, —(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)C(O)OR⁶, and the group:

wherein n independently represents an integer from 0 to 10 and R⁵independently represents hydrogen, linear and branched C₁-C₁₀ alkyl,linear and branched, C₂-C₁₀ alkenyl, linear and branched C₂-C₁₀ alkynyl,C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, and C₇-C₂₄ aralkyl; R⁶ represents aradical selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃,—CH(R⁷)OC(CH₃)₃, dicyclopropylmethyl, dimethylcyclopropylmethyl, or thefollowing cyclic groups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup; R¹ and R⁴ together with the two ring carbon atoms to which theyare attached can represent a substituted or unsubstituted cycloaliphaticgroup containing 4 to 30 ring carbon atoms, a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms andcombinations thereof; R¹ and R⁴ can be taken together to form thedivalent bridging group, —C(O)—Q—(O)C—, which when taken together withthe two ring carbon atoms to which they are attached form a pentacyclicring, wherein Q represents an oxygen atom or the group N(R⁸), wherein R⁸is selected from hydrogen, halogen, linear and branched C₁-C₁₀ alkyl, orC₆-C₁₈ aryl.
 91. The process of claim 90 further comprises at least onemultifunctional polycycloolefinic crosslinking monomer.
 92. The processof claim 91 wherein said multifunctional polycycloolefinic crosslinkingmonomer contains at least two polymerizable norbornene-type double bondsin its structure.
 93. The process of claim 92 wherein said crosslinkingmonomer is selected from the group consisting of the formulae:

and mixtures thereof, wherein m independently is an integer from 0 to 5and R⁹ is a divalent radical selected from alkylene, aromatic, or etherradicals.
 94. The process of claim 83 wherein said polymer is post curedat elevated temperature for at least one hour.
 95. The process of claim78 wherein said procatalyst is selected from the group consisting of(allyl)palladium(tricyclohexylphosphine)triflate,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate,(allyl)palladium(tri-o-tolylphosphine)triflate,(allyl)palladium(tri-o-tolylphosphine)trifluoroacetate,(allyl)palladium(trinaphthylphosphine)triflate, and(allyl)palladium(trinaphthylphosphine)trifluoroacetate.
 96. The processof claim 95 wherein said WCA salt is selected from the group consistingof lithium tetrakis(perfluorophenyl)borate and sodiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
 97. The process of claim96 wherein said WCA salt is (lithium 2.5 Et₂O)tetrakis(perfluorophenyl)borate.